CN112573636B - Method for treating organic pollutants by using iron-manganese ferrite-gold nano catalyst - Google Patents
Method for treating organic pollutants by using iron-manganese ferrite-gold nano catalyst Download PDFInfo
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- CN112573636B CN112573636B CN202011438283.XA CN202011438283A CN112573636B CN 112573636 B CN112573636 B CN 112573636B CN 202011438283 A CN202011438283 A CN 202011438283A CN 112573636 B CN112573636 B CN 112573636B
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Abstract
The invention discloses a method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, which is characterized in that the ferromanganese ferrite-gold nano catalyst is adopted to treat the organic pollutants, wherein the ferromanganese ferrite-gold nano catalyst comprises a ferromanganese ferrite, nano-gold particles and negative-valence gold ions, and the nano-gold particles and the negative-valence gold ions are jointly deposited on the surface of the ferromanganese ferrite. Compared with an MFO monomer and a nano gold colloid catalyst, the iron-manganese oxide-gold nano catalyst adopted in the invention has the advantages of good economic benefit, good stability, high catalytic activity, good recycling performance, easy recycling and the like, can be widely used as an economic ferrite-gold nano catalyst, can efficiently degrade and remove organic pollutants in the environment, particularly can degrade tetracycline antibiotics, and has good application value and application range.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation, relates to a method for degrading organic pollutants, and particularly relates to a method for treating organic pollutants by using a ferrite-gold nano catalyst.
Background
With the continuous development of industrial technology, the pollution of organic pollutants in the environment is more and more serious. For example, the emergence of antibiotics has made a very important contribution to the treatment of diseases, but due to the abuse of antibiotics, a large amount of antibiotics flows into the environment with sewage, and many rivers and lakes detect antibiotic pollution to different degrees, thus seriously threatening human health. In the case of Tetracycline (TC), a broad-spectrum antibiotic of formula C22H24N2O8It has effects in inhibiting gram-positive and gram-negative bacteria, killing bacteria at high concentration, and inhibiting rickettsia and trachoma virus. The tetracycline antibiotics mainly comprise aureomycin, oxytetracycline and tetracycline, wherein the aureomycin and the oxytetracycline are derivatives of the tetracycline, the former is clocycline, the latter is oxytetracycline, and the tetracycline family is acid-base amphoteric compounds. The tetracycline antibiotics are frequently detected in environmental water due to the large use of the tetracycline antibiotics in animal husbandry and human disease treatment, and the antibiotics are enriched to human bodies along with food chains, so that the health of the human bodies is threatened. On the other hand, tetracycline antibiotics in water are difficult to biodegrade, and a large amount of accumulated tetracycline can cause drug resistance and resistance genes. Therefore, how to reduce the environmental pollution caused by tetracycline antibiotics and prevent the substances from harming human and animals attracts people's attention.
At present, the treatment of tetracycline antibiotic wastewater at home and abroad mainly comprises physical, chemical and biological methods, mainly comprising physical chemical adsorption, biodegradation and the like, but because the structure of the tetracycline antibiotic is complex and stable, the methods are difficult to completely degrade the tetracycline in the wastewater, and the final product can generate secondary pollution if the tetracycline antibiotic cannot be completely degraded. The light Fenton technology is developed on the basis of the traditional Fenton reaction, and is a novel advanced oxidation technology which utilizes natural energy such as sunlight and the like as auxiliary energy so as to efficiently degrade organic pollutants in a water bodyProvided is a technique. In a homogeneous photo-Fenton reaction, Fe2+Catalytic hydrogen peroxide (H)2O2) Generating active free radical (hydroxyl free radical, OH) with strong oxidizing property to oxidize organic pollutants in water body, thereby achieving the purpose of degrading the organic pollutants, and promoting Fe by using a light source as an assistant in the reaction2+The reduction and regeneration of the catalyst are realized, so that the generation of sludge is reduced, and the catalyst is recycled. However, Fe is present in the homogeneous photo-Fenton reaction2+Low regeneration efficiency, narrow adaptable pH range and the like, which limits further application. Therefore, researchers developed heterogeneous photo-Fenton technology using Fe-containing solid catalyst as Fenton reagent to promote H2O2OH is produced by decomposition, Fe in the presence of light2+The regeneration is obtained on the surface of the catalyst, and simultaneously, the pH adaptation range of the solid catalyst is expanded due to the stable structure of the solid catalyst. Under the circumstances, the development of a heterogeneous photo-Fenton catalyst which is simple to prepare, efficient, green and safe is a precondition for the practical application of the technology.
Ferrite (MnFe)2O4MFO) is a good photo-fenton material, but it has the defects of easy precipitation, low absorption and utilization rate of light, low photo-fenton catalytic activity, and the like, which also limits its wide application in the heterogeneous photo-fenton catalytic field. Therefore, finding a suitable method to improve the photo-Fenton activity of MFO is of great significance to the development of efficient heterogeneous photo-Fenton catalytic materials and the application of the materials in the treatment of organic pollution of water bodies.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide the method for treating the organic pollutants by using the iron-manganese ferrite-gold nano catalyst, which has the advantages of simple operation, high efficiency, stable catalyst, easy recycling and economy.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst is characterized in that the ferromanganese ferrite-gold nano catalyst is used for treating the organic pollutants; the iron-manganese ferrite-gold nano catalyst comprises iron-manganese ferrite, nano gold particles and negative-valence gold ions, wherein the nano gold particles and the negative-valence gold ions are jointly deposited on the surface of the iron-manganese ferrite.
In the method, the total content of the nano gold particles and the negative gold ions in the ferromanganese ferrite-gold nano catalyst is further improved to be 1.15-3.92 wt%; the ferrite is nano-particles with the particle size of 20 nm-100 nm.
In the method, a further improvement is that the preparation method of the ferrite-gold nano catalyst comprises the following steps:
s1, mixing ferrite with ultrapure water, performing ultrasonic treatment, and adding Au3+Stirring the solution to obtain the iron manganese ferrite-Au3+A dispersion liquid;
s2, and mixing the ferrite-Au obtained in the step S13+The dispersion liquid is put under the condition of illumination for reduction reaction, and N is introduced2Removing O in solution2And meanwhile, adding a sacrificial agent, continuing to react, filtering, cleaning and drying to obtain the ferrite-gold nano catalyst.
In the above method, further modified, in step S1, the method for preparing the iron-manganese ferrite includes the following steps:
(1) mixing Fe3+Solution with Mn2+Mixing the solution and stirring to obtain Fe3+And Mn2+The mixed solution of (1);
(2) adjusting the Fe obtained in step (1)3+And Mn2+The pH value of the mixed solution is alkaline, water is added for dilution, the mixed solution is placed in a reaction kettle for reaction, and the ferric manganese ferrite is obtained after washing and drying.
In a further improvement of the above process, in step (1), the Fe3+And Mn2+Fe in the mixed solution of3+、Mn2+The molar ratio of (A) to (B) is 2: 1; the rotating speed of the stirring is 400 r/min-600 r/min; the stirring time is 10min to 30 min;
in the step (2), NaOH solution is adopted to adjust Fe under the stirring condition3+And Mn2+The pH value of the mixed solution is 11-12; the addition amount of the water is 20 mL-40 mL; said stirring beingThe rotating speed is 400 r/min-600 r/min; the reaction is carried out at the temperature of 170-190 ℃; the reaction time is 9-11 h.
In the step S1, the ratio of the ferrite to the ultrapure water is 400 mg: 40 mL-60 mL; the ferrite and Au3+The ratio of the solution is 400 mg: 1 mL-5 mL; the Au layer3+The solution is chloroauric acid solution; the Au layer3+The concentration of the solution is 10 g/L; the ultrasound is carried out at the temperature of 5-40 ℃; the ultrasonic time is 30-60 min; the rotating speed of the stirring is 400 r/min-600 r/min; the stirring time is 15 min;
in step S2, N is introduced after the reduction reaction is carried out for 1h2(ii) a The general formula N2Continuously introducing for 15-20 min; the iron manganese ferrite-Au3+The volume ratio of the dispersion liquid to the sacrificial agent is 41-65: 20-30; the sacrificial agent is at least one of methanol, formic acid, ammonium oxalate and ethanol; after the sacrificial agent is added, the reaction is continued for 2 to 3 hours; the reduction reaction is carried out under the stirring condition with the rotating speed of 400 r/min-1500 r/min.
In the method, the organic pollutants in the water body are treated by adopting the iron-manganese ferrite-gold nano catalyst, and the method is further improved and comprises the following steps: mixing the iron-manganese ferrite-gold nano catalyst with water containing organic pollutants by ultrasound, stirring, adding a hydrogen peroxide solution for a photo-Fenton oxidation degradation reaction, and finishing the treatment of the organic pollutants in the water.
In the method, the initial mass ratio of the iron-manganese ferrite-gold nano catalyst to the organic pollutants in the system of the photo-Fenton oxidation degradation reaction is 2.5-10: 1, and H is2O2The initial ratio of the organic pollutants is 1 mmol-8 mmol: 1 mg-4 mg.
In the method, further improvement is that the organic pollutant in the water body containing the organic pollutant is at least one of antibiotics, dyes and phenols; the antibiotic is a tetracycline antibiotic; the tetracycline antibiotic is at least one of tetracycline, oxytetracycline and chlortetracycline; the dye is methyl orange and/or Congo red; the phenols are nitrophenol and/or phenol; the concentration of the organic pollutants in the water body containing the organic pollutants is 10 mg/L-40 mg/L; the pH value of the water body containing the organic pollutants is 3-9.
In the above method, further improvement, the stirring is performed under dark conditions; the stirring time is 20 min-60 min; the photo-Fenton oxidation degradation reaction is carried out under the illumination condition with the wavelength of 300 nm-800 nm; the rotating speed is controlled to be 300 r/min-900 r/min in the photo-Fenton oxidation degradation reaction process; the time of the photo-Fenton oxidative degradation reaction is 30-120 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating organic pollutants by using a ferrite-gold nano catalyst, which takes the ferrite-gold nano catalyst as a catalyst of a photo-Fenton degradation reaction to carry out oxidation catalysis treatment on the organic pollutants, thus realizing effective removal of the organic pollutants. In the case of Tetracycline (TC), in small amounts of H2O2Fe in the presence of a ferrimanganite-gold nanocatalyst2+/Fe3+、Mn2+/Mn3+、Au0/Auδ-Oxidation-reduction potential pair catalytic decomposition of H2O2Can generate a large amount of OH to realize the degradation of organic pollutants, and the specific process is that rich surface hydroxyl and Au (Au) with negative valence are contained in the ferrimanganite-gold nano catalystδ-) Is favorable to H2O2Adsorption of, on the one hand, Fe in Fermanoxysome-gold nanocatalysts2+、Mn2+And Auδ-Produce synergistic effect and promote H2O2A large amount of OH is generated by decomposition, organic pollutants can be degraded, and corresponding Fe is generated at the same time3+、Mn3+And Au0(ii) a On the other hand, inUnder the condition of visible light, the gold nanoparticles are excited to generate 'hot electrons', and the 'hot electrons' generated under the plasma resonance effect are transferred from the gold nanoparticles to the MFO, so that the absorption of the MFO to light is promoted, and the generation of photon-generated carriers is promoted. Under visible light, MFO is excited by light to generate electron and hole recombination pairs, and the conduction band position of MFO is +0.69eV, and the ratio of MFO to H is2O2The redox potential (0.38eV) of OH is corrected, so that the holes generated at the position of the conduction band on the one hand directly oxidize and degrade TC and on the other hand promote H2O2Decomposition to generate superoxide radical (. O)2 -) Degrading TC. At the same time, electrons generated at the valence band of MFO can reduce the metal element to promote Fe2+、Mn2+And Auδ-Regeneration of (2); and electrons generated on the valence band of the MFO are more negative than the Fermi level (+0.5eV) of the nanogold, so the electrons on the MFO can be transferred to the nanogold, the service life of a photon-generated carrier is prolonged, and the catalytic efficiency is improved. In another aspect, MFO and Au in the present invention Ferro-manganese ferrite-gold nanocatalystδ-All have the function of Fenton reagent, can further promote the generation of OH and improve the catalytic efficiency. The MFO, the nano gold particles and the negative-valence gold ions in the iron-manganese ferrite-gold nano catalyst are interacted to jointly promote the improvement of the catalytic activity, so that the iron-manganese ferrite-gold nano catalyst has higher photo-Fenton catalytic activity. Compared with an MFO monomer and a nano gold colloid catalyst, the iron-manganese oxide-gold nano catalyst adopted in the invention has the advantages of good economic benefit, good stability, high catalytic activity, good recycling performance, easy recycling and the like, can be widely used as an economic ferrite-gold nano catalyst, can efficiently degrade and remove organic pollutants in the environment, particularly can degrade tetracycline antibiotics, and has good application value and application range.
The whole process includes two mechanisms, namely Fenton-like (formula 1-2) and photocatalysis (formula 3-7), as follows:
Fe2+/Mn2+/Auδ-+H2O2+H+→·OH+Fe3+/Mn3+/Au0+H2O (1)
OH + organic contaminants → intermediates + CO2+H2O (2)
Au+hγ(visible)→Au(e-)+Au(h+) (3)
Au(e-)+MFO→MFO(e-)+Au (4)
MFO+hγ(visible)→MFO(e-)+MFO(h+) (5)
MFO(h+) + organic contaminants → intermediates + CO2+H2O (6)
Fe3+/Mn3+/Au0+e-→Fe2+/Mn2+/Auδ- (7)
(2) In the invention, the adopted ferromanganese ferrite-gold nano catalyst comprises ferromanganese ferrite (MFO), nano gold particles and negative-valence gold ions (nano gold), and the MFO is used as octahedral spinel, has stable structure and magnetism, and is beneficial to separation from a solution; meanwhile, the MFO prepared from the method has wide sources and the characteristics of economy and low toxicity, but the light absorption capacity of the MFO is poor, so that the catalytic activity of the MFO is limited. The nano gold as a noble metal nano material has a special surface plasma resonance effect, is an electron acceptor and an electron pool, has strong light absorption capacity, but is expensive and not beneficial to wide preparation. Therefore, a small amount of nanogold is introduced into the iron-manganese ferrite-gold nano catalyst, and the defects of MFO and nanogold are combined, so that the iron-manganese ferrite-gold nano catalyst which is economical, low in toxicity and easy to recycle is obtained; and because of the light absorption capacity of the nano-gold, thermal electrons are generated under visible light, and the combination of the thermal electrons and the thermal electrons can promote the light absorption of the iron manganese oxide-gold nano-catalyst, so that the separation efficiency of light-excited electrons and holes of the catalyst is improved, the catalytic efficiency is promoted, and the catalytic activity of the iron manganese oxide-gold nano-catalyst prepared by the method is further improved.
(3) In the invention, the adopted ferromanganese ferrite-gold nano-catalyst optimizes the content of nano-gold (nano-gold particles and negative-valence gold ions) to be 1.15-3.92 wt%, improves the light absorption performance and the catalytic performance of the catalyst and simultaneously reduces the material cost, thereby obtaining the ferromanganese ferrite-gold nano-catalyst with high catalytic activity and low cost, because the content of the nano-gold in the catalyst has important influence on the catalytic performance of the catalyst. When the content of Au is too low (e.g. less than 1.15 wt%), the loading of the nano-gold particles is low, and the low amount of nano-gold is not favorable for light absorption, so that the photo-fenton activity is still poor; and when the content of nanogold is too high (for example, higher than 3.92 wt%), too much nanogold can be more easily precipitated, the particles are larger, the catalytic efficiency is influenced, meanwhile, when the content of Au is too high, the reduction of material cost is not facilitated, the actual requirement is difficult to meet, more importantly, too much nanogold is deposited on the surface of the ferrite, a compact protective layer can be formed on the surface of the ferrite, the Fenton reagent is not facilitated, the target pollutant enters the catalyst, and the target pollutant is difficult to be effectively removed by utilizing the Fenton reaction.
(4) According to the invention, the adopted ferromanganese ferrite-gold nano catalyst has an isoelectric point of 7.42, has wide pH adaptability, has high catalytic activity when the pH is 3-7, overcomes the defect of narrow pH adaptability range of the traditional Fenton reagent, and realizes high catalytic efficiency under a near-neutral condition.
(5) In the invention, when the adopted ferromanganese ferrite-gold nano catalyst is used for treating organic pollutants (such as TC), the stability and the Total Organic Carbon (TOC) removal rate are good, the catalyst can be repeatedly utilized for many times, and the removal rate is still as high as 85.42% after the catalyst is repeatedly used for 5 times, so that the treatment cost is favorably reduced, and the catalytic activity is good.
(6) The preparation method of the iron-manganese ferrite-gold nano catalyst is prepared by a photoreduction synthesis method, and specifically comprises the following steps: firstly taking ferrite as a carrier, and Au3+Mixing the solutions to prepare the ferrite-Au3+Dispersing the Au in the solution, then carrying out reduction reaction under the condition of illumination, and reacting the Au under the action of a sacrificial agent3+Reduction to Au0And Auδ-And depositing on the surface of the ferrite to form ferrite-goldRice catalyst. In the invention, MFO contains abundant surface hydroxyl, and the existence of surface oxygen is favorable for Au3+Adsorbed on the surface of MFO, under the irradiation of light, MFO generates electron-hole pairs, and then the holes generated by MFO are captured under the existence of sacrificial agent, so that adsorbed Au is obtained3+Is reduced to Au under the action of MFO residual electrons0And Auδ-And the catalyst is firmly combined on the surface of MFO, so that the iron-manganese ferrite-gold nano catalyst with good stability and high catalytic activity is prepared. The preparation method has the advantages of wide raw material source, low cost, no need of special equipment and the like, is suitable for large-scale preparation, and is beneficial to industrial production.
(7) In the preparation method of the iron-manganese ferrite-gold nano catalyst, the reduction reaction is carried out under the conditions of ultraviolet light and visible light, namely, the reduction reaction can be carried out by utilizing the irradiation of sunlight, and the preparation method has the characteristics of energy conservation and green; the adopted sacrificial agent can be at least one of methanol, formic acid, ammonium oxalate and ethanol, the applicability is wide, and the preparation method and the prepared iron-manganese ferrite-gold nano-catalyst can be further promoted.
(8) In the preparation method of the iron-manganese ferrite-gold nano catalyst adopted in the invention, the adopted iron-manganese ferrite is Fe3+Solution and Mn2+The solution is respectively used as the source of Fe and Mn and is prepared by adopting a coprecipitation method, wherein Fe is adopted3+And Mn2+The solution may be Fe-containing3+And Mn2+The wastewater has the advantages of wide raw material source, low cost and the like, and accords with the concept of waste recycling. In addition, Fe3+And Mn2+Fe in the mixed solution of3+、Mn2+The molar ratio of (a) has a very important influence on the formation of the ferrite monomer. The molecular formula of the ferrite is MnFe2O4Therefore, the molar ratio of Fe to Mn is 2: 1, and an octahedral spinel structure having a stable structure is formed, and if the ratio of Fe to Mn is not 2: 1, Fe is liable to be present3O4、Fe2O3And MnO2And the impurities are not beneficial to the proceeding of the photo-Fenton reaction on one hand, and can seriously affect the stability and the recycling performance of the catalyst on the other hand.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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.
FIG. 1 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And XRD patterns of ferrite (MFO).
FIG. 2 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And TEM images of iron manganese oxides (MFO).
FIG. 3 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And SEM images of ferrite (MFO).
FIG. 4 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And XPS comparison of ferrite (MFO).
FIG. 5 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) Au high resolution XPS plot of (a).
FIG. 6 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And an adsorption-desorption isotherm diagram of ferrite (MFO).
FIG. 7 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And pore size distribution of ferrite (MFO).
FIG. 8 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And VSM Maps of Ferrite (MFO).
FIG. 9 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And characterization of the photochemical properties of ferrite (MFO).
FIG. 10 shows different Ferro-Mn ferrite-gold nanocatalysts and different systems (H) in example 1 of the present invention2O2/Vis、MFO/H2O2/Vis、MFO-Au(3)/H2O2And MFO-Au(3)Per Vis) degradation effect on TC.
FIG. 11 shows different Ferro-Mn ferrite-gold nanocatalysts and different systems (H) in example 1 of the present invention2O2/Vis、MFO/H2O2/Vis、MFO-Au(3)/H2O2And MFO-Au(3)Vs) corresponding kinetic constants for degradation of TC.
Fig. 12 is a TOC degradation diagram corresponding to different iron-manganese ferrite-gold nano-catalysts degrading TC under different systems in example 1 of the present invention.
Fig. 13 is a graph of the effect of cyclic degradation of TC by the ferrite-gold nanocatalyst in example 2 of the present invention.
FIG. 14 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) XRD pattern of (a).
FIG. 15 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) FT-IR diagram of (1).
FIG. 16 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) The XPS chart (a) shows Fe 2p, (b) shows Mn 2p, (c) shows Au 4f, and (d) shows O1 s.
FIG. 17 shows the example 3 of the present invention in which the ferrite-gold nano-catalyst (MFO-Au)(3)) Degradation profiles for different tetracycline antibiotics.
FIG. 18 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) in example 4 of the present invention(3)) At different contents of H2O2Degradation profile of TC under conditions.
FIG. 19 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) in example 4 of the present invention(3)) At different contents of H2O2Kinetic constant plots of corresponding TC under the conditions.
Fig. 20 is a graph of degradation of the ferrite-gold nanocatalyst under different initial pH conditions in example 5 of the present invention for TC.
Fig. 21 is a graph showing degradation of different concentrations of TC by the ferrite-gold nanocatalyst in example 6 of the present invention.
Fig. 22 is a graph showing degradation of the iron-manganese ferrite-gold nano-catalyst in different water bodies in example 7 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the examples of the present invention, the raw materials and instruments used were all commercially available. If not stated otherwise, the process adopted is a conventional process, the equipment adopted is conventional equipment, and the obtained data are average values of more than three repeated experiments.
Example 1
A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, in particular to a method for treating Tetracycline (TC) in a water body by using the ferromanganese ferrite-gold nano catalyst, which comprises the following steps:
taking iron-manganese ferrite-gold nano catalyst (MFO-Au)(1)、MFO-Au(2)、MFO-Au(3)、MFO-Au(4)、MFO-Au(5)) 10mg of the solution is added into 100mL of TC solution with the concentration of 20mg/L (the pH value of the solution is 6.0), stirred under the dark condition (the rotating speed can be 400 r/min-600 r/min, such as 500r/min) for 30min to reach the adsorption balance, and then 5mL of H with the concentration of 1M is added under the irradiation of visible light2O2And (5) carrying out a photo-Fenton catalytic oxidation reaction on the solution for 90min to finish the degradation of TC.
In this example, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(1)) The nano-gold-ferrite-based composite material comprises a ferrite, nano-gold particles and negative-valence gold ions, wherein the nano-gold particles and the negative-valence gold ions are jointly deposited on the surface of the ferrite. The total content of nano gold particles and negative gold ions in the iron-manganese ferrite-gold nano catalyst is 1.15 wt%; the molecular formula of the ferrite is MnFe2O4. The ferrite is a sphere-like and irregular cube, is a nano particle, and has an average particle size of 20-100 nm.
In this example, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(1)) The preparation method comprises the following steps:
(1) preparation of ferrite
(1.1) 2.7029g of chlorine were weighedIron sulfide (FeCl)3·6H2O) and 0.9892g of manganese chloride (MnCl)2·4H2O) the solids were dissolved in 15mL of ultrapure water, respectively, to obtain a solution containing Fe3+And Mn2+And slowly mixing them, and continuously stirring at 500r/min for 20min to obtain Fe3+And Mn2+The mixed solution of (1).
(1.2) reacting Fe obtained in the step (1.1)3+And Mn2+The mixed solution is continuously stirred at the rotating speed of 500r/min, NaOH solution (10mL, 0.08mol/L) is added dropwise, the pH of the mixed solution is adjusted to 11-12, and the alkaline Fe is obtained3+And Mn2+The mixed solution of (1).
(1.3) basic Fe obtained in the previous step (1.2)3+And Mn2+Adding a certain amount of ultrapure water into the mixed solution for dilution, fixing the volume to 60mL, transferring the mixed solution into a polytetrafluoroethylene reaction kettle (the volume is 100mL), reacting for 10 hours at 180 ℃, cooling the mixed solution after reaction, washing with ultrapure water and ethanol, and drying to obtain the ferrite (MFO).
(2) Preparation of ferrite-gold nano-catalyst
(2.1) taking 400mg of the ferrite-manganese oxide (MFO) obtained in the step (1), adding 40mL of ultrapure water, performing ultrasonic treatment at 25 ℃ for 30min, continuously stirring at the rotating speed of 500r/min after dispersion, adding 1mL of chloroauric acid solution (the chloroauric acid solution is dissolved in 1g of chloroauric acid in a 100mL volumetric flask at room temperature to be constant volume, and the concentration is 10g/L), and fully stirring for 15min to ensure that Au is dissolved in the solution3+Adsorbing on ferrite monomer to obtain ferrite-Au3+And (3) dispersing the mixture.
(2.2) under the condition of continuous stirring (the rotating speed is 1000r/min), the ferro-manganese ferrite-Au obtained in the step (2.1)3+The dispersion is put under ultraviolet light for reduction reaction, and N is introduced after 1 hour2The time is 15min to remove O in the solution2Simultaneously adding 20mL of methanol as a sacrificial agent, continuously reacting for 2h, filtering, cleaning with ultrapure water and ethanol, drying, washing for 3 times respectively, and drying in a 60 ℃ oven to obtain the ferrite-gold nano catalyst, which is marked as MFO-Au(1)。
In this example, the iron manganese ferrite-gold nanocatalyst was usedOxidizing agent (MFO-Au)(2)) With MFO-Au(1)Essentially the same, differing only in that: MFO-Au(2)The total content of the medium-sized gold nanoparticles and the negative-valent gold ions is 2.45 wt%. MFO-Au(2)The amount of the chloroauric acid solution added in the preparation method of (1) was 2 mL.
In this example, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(3)) With MFO-Au(1)Essentially the same, differing only in that: MFO-Au(3)The total content of the medium-sized gold nanoparticles and the negative-valent gold ions is 3.43 wt%. MFO-Au(3)The amount of the chloroauric acid solution added in the preparation method of (1) was 3 mL.
In this example, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(4)) With MFO-Au(1)Essentially the same, differing only in that: MFO-Au(4)The total content of the medium-sized gold nanoparticles and the negative-valence gold ions is 3.86 wt%. MFO-Au(4)The amount of the chloroauric acid solution added in the preparation method of (1) was 4 mL.
In this example, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(5)) With MFO-Au(1)Essentially the same, differing only in that: MFO-Au(5)The total content of the medium-sized gold nanoparticles and the negative-valence gold ions is 3.92 wt%. MFO-Au(5)The amount of the chloroauric acid solution added in the preparation method of (1) was 5 mL.
FIG. 1 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And XRD patterns of ferrite (MFO). As can be seen from FIG. 1, the iron manganese oxide (MFO) shows complete diffraction peaks at 18.12 °, 29.72 °, 35.00 °, 36.62 °, 42.50 °, 52.74 °, 56.22 °, 61.64 ° and 72.98 °, indicating (111), (220), (311), (222), (400), (422), (511), (440) and (533) planes (JCPDS No.10-0319) of the MFO, respectively, while MFO-Au shows(3)Diffraction peaks at 38.14 °, 44.42 °, 64.56 ° and 77.64 ° belong to (111), (200), (220) and (311) planes of nanogold (JCPDS No. 04-0784). When the nano-gold is deposited, the crystal lattice of MFO is not affected, and XRD data proves that MFO and MFO-Au are not affected(3)Not only the synthesis is successful, but also the purity is higher.
FIG. 2 shows the Ferro-Mn ferrite-gold nano-catalyst (MF) prepared in example 1 of the present inventionO-Au(3)) And TEM images of iron manganese oxides (MFO). FIG. 3 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And SEM images of ferrite (MFO). As can be seen from FIGS. 2a and 3a-b, MFO is a spherical-like particle and irregular cube of size 20nm to 100nm, which is a type of nanoparticle; however, when gold is deposited on the MFO surface, the irregular cubes occupy the major portion and increase in size to 20 nm-200 nm (fig. 2d and 3 d-e). As can be seen from the ESD tests of FIGS. 3c and 3f, the MFO contains Fe, Mn and O elements, and the molar ratio of Fe to Mn is close to 2: 1, which proves the successful synthesis of the MFO; MFO-Au(3)Also contains Fe, Mn, O and Au elements, and proves the successful synthesis of MFO-Au and basically loads/bonds on the MFO surface. The SAED plot of the MFO in fig. 2b shows a clear point-ring plot, demonstrating that the MFO is a perfect face-centered cubic structure with lattices 4.848, 3.077, 2.564, 2.174, 1.780, 1.671, and
the planes of (a) and (b) are perfectly matched to the (111), (220), (311), (400), (422), (511) and (440) planes of the MFO, which is also consistent with the XRD pattern of the MFO (fig. 1); MFO-Au(3)In high resolution TEM image (FIG. 2e)
The crystal lattice of (311) is clearly visible, meaning the presence of the (311) plane in MFO, whereas the crystal lattice of the nano-gold particles is difficult to find, because of the low Au content. The presence of the Au element is clearly visible in the HAADF-STEM, thus further demonstrating the successful deposition of Au (fig. 2c and 2 f).
FIG. 4 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And XPS comparison of ferrite (MFO). Wherein FIG. 4a is a full spectrum XPS chart, MFO contains Fe, Mn and O elements, MFO-Au(3)The composite material contains Fe, Mn, O and Au elements, and further proves the successful synthesis of MFO-Au. FIGS. 4b-d are high resolution XPS plots of O, Fe and Mn, respectively. As can be seen from the b diagram, the binding energy peaks of O in MFO are mainly 529.75 and 531.70eV, which respectively mean the presence of Fe-O and Mn-O, surface hydroxyl groups and oxygen in adsorbed oxygen (i.e., O)Latt、OHydAnd OAds). After gold deposition, OLattIs reduced in content of (A) and (B), and OHydAnd OAdsIs increased, possibly due to the insertion of a portion of Au into the lattice of MFO. As can be seen from FIG. c, the MFO peaks at 710.05, 711.75, 723.50 and 725.30eV respectively represent Fe 2p3/2And Fe 2p1/2And peak pairs at 710.05 and 725.30eV and 711.75 and 723.50eV respectively represent Fe2+And Fe3+. The satellite peak at 718.80eV is due to Fe3+Is present. For the high resolution spectrum of Mn 2p (panel d), there are three typical peaks located at 640.70, 642.15, and 652.85eV, respectively, indicating the presence of Mn 2p in MFO3/2And Mn 2p1/2. At Mn 2p3/2The peaks at 640.70 and 642.15eV indicate Mn2+And Mn3+The concomitant peak at 645.10eV is due to Mn2+Is present. Meanwhile, the deposition of Au has little influence on the valence states of Fe and Mn, which is consistent with the results of XRD.
FIG. 5 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) Au high resolution XPS plot of (a). As can be seen from FIG. 5, the characteristic peaks of Au have two peaks at 88.00eV and 84.25eV, which demonstrates that Au is present0I.e. the presence of nanogold, Au0Can form Au in the reaction process0/Auδ+The oxidation-reduction potential pair promotes H2O2Decomposition of (2); meanwhile, a small peak is formed at 83.10eV, and a small part of the negative valence gold (Au) is proved to be presentδ-) Is present. Au coatingδ-On the one hand in favor of H2O2On the other hand with Au0Formation of Auδ-/Au0Redox potential pair, favouring the generation of H2O2Decomposed to OH.
FIG. 6 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And an adsorption-desorption isotherm diagram of ferrite (MFO). As can be seen from FIG. 6, MFO and MFO-Au(3)All conform to IUPAC type IV adsorption and carry H3Hysteresis indicating that both contain abundant mesopores. When Au is deposited, the BET specific surface area, the total pore volume and the average pore diameter of the material are changed only slightlyIt shows that the Au deposition has less influence on the MFO.
FIG. 7 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And pore size distribution of ferrite (MFO). As can be seen from fig. 7, when Au was deposited, the pore size contribution in the material shifted from 22.27nm alone to 3.56 and 30.68nm, indicating that the presence of Au also increased the mesoporosity of the material.
FIG. 8 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And VSM Maps of Ferrite (MFO). As can be seen from FIG. 8, MFO and MFO-Au(3)All have strong magnetism, and the catalyst can be separated from the solution by using a magnet, thereby being beneficial to the recycling of the catalyst.
FIG. 9 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) prepared in example 1 of the present invention(3)) And characterization of the photochemical properties of ferrite (MFO). FIG. 9a is a Fourier transform infrared spectroscopy (FT-IR) plot at 1388cm-1And 1540cm-1The characteristic peaks at (a) are due to the presence of surface hydroxyl groups and Bronsted sites on the MFO, and there is a slight decrease in intensity of these two characteristic peaks after the Au photo-deposition, indicating that some of the Bronsted sites may be occupied by Au, while some of the surface hydroxyl groups are consumed during the Au deposition. The presence of hydroxyl groups on the surface of the material can promote the formation of OH although MFO-Au(3)The surface hydroxyl is reduced, but the formed negative valence gold is beneficial to H2O2Decomposition of (D) to form OH. Compared with reduced surface hydroxyl, the advantage of more deposited negative-valence gold is more obvious, and therefore, the deposition of Au is beneficial to the improvement of the photo-Fenton catalytic efficiency. FIG. 9b is a graph of the diffuse reflectance of ultraviolet (UV-vis DRS), clearly MFO and MFO-Au(3)Has a wide light absorption range in the range of 200-800nm, and MFO-Au(3)Is stronger, which is beneficial for the increase of the light absorption of the material. As can be seen from FIG. 9c, the band gap energy of MFO calculated by the Kubelka-Munk function is 1.58 eV; from FIG. 9d, the valence band of MFO is +0.69eV and the conduction band is-0.89 eV as analyzed and calculated from the Mott-Schottky data, and the MFO is a p-type semiconductor as shown in the M-S diagram; from the EIS diagram of FIG. 9e, the MFO-Au is shown(3)Is less than the MFO, and the light of fig. 9fCurrent testing then demonstrated that photo-deposited Au can facilitate the separation of electrons and holes in MFO. These data indicate MFO-Au(3)Has better photoresponse capability and higher efficiency of degrading organic pollutants by light Fenton.
FIG. 10 shows different Ferro-Mn ferrite-gold nanocatalysts and different systems (H) in example 1 of the present invention2O2/Vis、MFO/H2O2/Vis、MFO-Au(3)/H2O2And MFO-Au(3)Per Vis) degradation effect on TC. FIG. 11 shows different Ferro-Mn ferrite-gold nanocatalysts and different systems (H) in example 1 of the present invention2O2/Vis、MFO/H2O2/Vis、MFO-Au(3)/H2O2And MFO-Au(3)Vs) corresponding kinetic constants for degradation of TC. Fig. 12 is a TOC degradation diagram corresponding to different iron-manganese ferrite-gold nano-catalysts degrading TC under different systems in example 1 of the present invention. As can be seen from FIG. 10, under visible light, when only MFO-Au is present(3)Or H2O2The TC can not be degraded when the single-component composite material exists alone, the TC can be effectively degraded only when the two-component composite material exists simultaneously, and 88.34 percent of the TC can be degraded within 90 min. MFO/H2O2Vis and MFO-Au3/H2O2The degradation efficiency of TC under the system is 55.48% and 61.65% respectively, which means that the visible light Fenton degradation efficiency of the MFO monomer to the TC is low, and the existence of Au greatly improves the catalytic efficiency; on the other hand, the photo-Fenton catalytic efficiency of the system is obviously improved under the condition of visible light, which also indicates the importance of Au and visible light for degrading TC in the system. At the same time, in MFO-Au3/H2O2The degradation rate constant (k) under the Vis system is 0.0231min-1Much higher than other systems. This is also consistent with the trend in TOC removal efficiency (fig. 12). On the other hand, when the content of Au is increased, the degradation efficiency of the ferromanganese ferrite-gold nano-catalyst is increased, and MFO-Au(3)The best TC degradation efficiency is exhibited. However, with further increase of Au content, the degradation efficiency of the ferrimanganite-gold nanocatalyst is rather decreased, which is probably because of MFO when Au content reaches 3.46%The loading sites have reached saturation and thus the loaded Au is lost, and at the same time, part of the chloroauric acid is lost during the reduction, as also evidenced by ICP-OES data. In addition, as can be seen from fig. 11, the catalytic reduction reactions corresponding to the fe-mn-Au nanocatalyst of the present invention all meet the first order kinetics, and the fe-mn-Au nanocatalyst (MFO-Au)(1)、MFO-Au(2)、MFO-Au(3)、MFO-Au(4)、MFO-Au(5)) The corresponding kinetic constants are: k1＝0.0149min-1、K2＝0.0182min-1、K3＝0.0231min-1、K4＝0.0161min-1、K5＝0.0131min-1。
Example 2
Investigation of Ferro-manganese ferrite-gold nanocatalyst (MFO-Au)(3)) The stability of organic pollutants is treated, specifically Tetracycline (TC) in a water body is treated by adopting a ferrimanganite-gold nano catalyst, and the method comprises the following steps:
(1) 10mg of the iron-manganese-oxide-gold nano-catalyst (MFO-Au) prepared in example 1 was taken(3)) Adding into 100mL of 20mg/L TC solution (pH of the solution is 6.0), stirring under ultrasound in dark for 30min at 400-600 r/min (such as 500r/min), irradiating with visible light after adsorption balance is achieved, and adding 5mL of 1M H2O2And (3) fully mixing the solutions, and then carrying out a photo-Fenton oxidative degradation reaction for 90min to complete the treatment of TC.
(2) After the reaction in the step (1) is completed, filtering the solution after the reaction to obtain a solid substance (MFO-Au)(3)) Washing with ultrapure water and anhydrous ethanol, drying, and drying to obtain solid substance (MFO-Au)(3)) The TC solution was repeatedly treated according to the method in the step (1) for 5 times.
Fig. 13 is a graph of the effect of cyclic degradation of TC by the ferrite-gold nanocatalyst in example 2 of the present invention. As can be seen from FIG. 13, a manganese ferrite-gold nano-catalyst (MFO-Au) was used(3)) After the TC solution is circularly treated for 5 times, the removal rate of the TC is still as high as 85.42 percent, which indicates that the iron-manganese ferrite of the inventionGold nanocatalyst (MFO-Au)(3)) Has stronger stability and catalytic activity.
FIG. 14 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) XRD pattern of (a). FIG. 15 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) FT-IR diagram of (1). In FIGS. 14 and 15, post-reaction MFO-Au nanocatalyst (MFO-Au)(3)) Refers to the collected MFO-Au nano catalyst (MFO-Au) after 5 times of repeated use(3)). As can be seen from FIGS. 14 and 15, MFO-Au(3)The crystal phase mainly contains MFO and Au elements, and the crystal phase is not obviously changed after the reaction, and the MFO-Au is subjected to the reaction before and after the reaction(3)The FT-IR chart of (A) shows almost no change, indicating that the MFO-Au prepared by the invention(3)The catalyst has excellent stability.
FIG. 16 shows the Fe-Mn-O-Au nano-catalyst (MFO-Au) before and after the reaction in example 2 of the present invention(3)) High resolution XPS plots of (a). As can be seen from fig. 16, after 5 cycles, the XPS peak position of each element was not changed, and still maintained good stability, except that the relative proportion of the valence state of each element in the catalyst was slightly changed. In Fe 2p (FIG. 16a), indicates Fe 2p3/2The peak of the spectrum (B) is reduced at 710.25eV, and the peak of the spectrum (B) represents Fe at 719.00eV3+Has a rise in the satellite peak. Fe3+Increased from 62.25% to 68.38% relative proportion of Fe3+The relative proportion of (B) was reduced from 37.75% to 31.61%, indicating that there was a small proportion of Fe during the reaction2+Is changed into Fe3+. The peak at 642.40eV in the map of Mn 2p (FIG. 16b) was increased, and represents Mn2+Satellite peak at 645.80eV and represents Mn 2p3/2The peaks at 641.00eV are all weaker. Thus Mn3+The relative ratio of Mn increases from 27.02% to 31.79%, while Mn2+The ratio of (A) is reduced from 43.17% to 38.00%, indicating that the material contains a small amount of Mn2+After reaction, becomes Mn3+. As can be seen from FIG. 16c, Au was still present after the reaction0And Auδ-At 84.25eV represents Au 4f7/2Increased and at 88.00eV represents Au 4f7/2Sum positionRepresents Au at 83.10eVδ-All the peaks of (A) are reduced, and Au is calculated from the reduction0The relative proportion of the gold (II) is increased from 50.06% to 51.01%, while the relative proportion of the gold (II) is reduced from 49.94% to 48.99%, which shows that part of Au is present after the reactionδ-Conversion to Au0. The above results may be the reason for a slight decrease in the catalytic performance of the material after 5 cycles, but the results still indicate Fe2+/Fe3+、Mn2+/Mn3+And Au0/Auδ-Has better circulation, further proves the stability of the material.
Example 3
A method for treating organic pollutants by using a ferrite-gold nano catalyst is specifically to respectively treat Tetracycline (TC), aureomycin (CTC) and Oxytetracycline (OTC) in a water body by using the ferrite-gold nano catalyst, and comprises the following steps:
3 parts of the iron-manganese-oxide-gold nano-catalyst (MFO-Au) prepared in example 1 were taken(3)) Respectively adding 10mg of the above components into 100mL of TC, CTC and OTC solutions with concentration of 20mg/L (the pH values of the solutions are all 6.0), ultrasonically stirring (at the rotation speed of 400 r/min-600 r/min, such as 500r/min) for 30min under dark condition, irradiating with visible light after adsorption balance is reached, and simultaneously adding 5mL of H with concentration of 1M2O2And (3) fully mixing the solutions, and then carrying out a photo-Fenton oxidation degradation reaction for 90min to finish degradation treatment on each tetracycline antibiotic.
FIG. 17 shows the example 3 of the present invention in which the ferrite-gold nano-catalyst (MFO-Au)(3)) Degradation profiles for different tetracycline antibiotics. As can be seen from fig. 17, the concentrations of these tetracycline antibiotics (TC, CTC and OTC) decreased with time, degrading 88.34%, 83.07%, 82.02% within 90min, respectively; simultaneously, the reactions of the two compounds accord with first-order kinetics, and kinetic constants are respectively as follows: kTC＝0.0231min-1、KCTC＝0196min-1And KOTC＝0.0179min-1. The iron-manganese ferrite-gold nano catalyst in the method has higher oxidative catalytic degradation efficiency on tetracycline antibiotics and is widely suitable for the tetracycline antibioticsThe utility model is good in use property.
Example 4
A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, in particular to a method for treating Tetracycline (TC) in a water body by using the ferromanganese ferrite-gold nano catalyst, which comprises the following steps:
taking 8 parts of 100mL TC solution with the concentration of 20mg/L (the pH value of the solution is 6.0); 8 parts of 10mg of the iron-manganese-oxide-gold nanocatalyst (MFO-Au) prepared in example 1 were taken(3)) Adding into the TC solution, stirring in dark for 30min at 400-600 r/min (500 r/min) under ultrasonic condition, irradiating with visible light, and adding 1, 2, 3, 4, 5, 6, 7 and 8mL of H with concentration of 1M2O2Fully mixing the solution, and performing a photo-Fenton oxidative degradation reaction for 90min to complete the reaction on different H2O2Degradation treatment of TC in the presence of the catalyst.
FIG. 18 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) in example 4 of the present invention(3)) At different contents of H2O2Degradation profile of TC under conditions. As is clear from FIG. 18, in the first 10min after the start of the reaction, H was caused2O2The rapid decomposition of (2) makes the degradation speed of TC very fast, and the degradation speed gradually decreases with the time and finally tends to be flat. When H is present2O2The degradation rate of TC increased significantly from 1mmol to 5mmol and reached a maximum at 5mmol, indicating degradation of TC and H2O2The contents of (A) and (B) are closely related. When H is present2O2When the amount of (A) is further increased, due to excessive H2O2On the one hand, generated OH is removed, and on the other hand, MFO-Au is occupied(3)Resulting in a decrease in the degradation efficiency of TC. FIG. 19 shows a Fe-Mn-O-Au nano-catalyst (MFO-Au) in example 4 of the present invention(3)) At different contents of H2O2Kinetic constant plots of corresponding TC under the conditions. As can be seen from FIG. 19, in the presence of added H2O2When the amounts of the components are 1mmol, 2mmol, 3mmol, 4mmol, 5mmol, 6mmol, 7mmol and 8mmol, the kinetic constants corresponding to the degradation of TC are 0.0051min in this order-1、0.0063min-1、0.0076min-1、0.0088min-1、0.0231min-1、0.0196min-1、0.0154min-1And 0.0126min-1This is in accordance with the rule of fig. 18, so H is selected here2O2The amount of (B) is preferably 5 mmol.
Example 5
A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, in particular to a method for treating Tetracycline (TC) in a water body by using the ferromanganese ferrite-gold nano catalyst, which comprises the following steps:
taking 5 parts of 100mL TC solution with the concentration of 20mg/L, and respectively adjusting the pH values of the TC solution to 3, 5, 6, 7 and 9; 5 parts of 10mg of the iron-manganese-oxide-gold nanocatalyst (MFO-Au) prepared in example 1 were taken(3)) Adding into the TC solutions under different pH conditions, ultrasonically stirring (at 400-600 r/min, such as 500r/min) in dark for 30min to reach adsorption balance, irradiating with visible light, and adding 5mL of 1M H2O2And (3) fully mixing the solutions, and then carrying out a photo-Fenton oxidative degradation reaction for 90min to finish the degradation treatment of TC under different pH conditions.
Fig. 20 is a graph of degradation of the ferrite-gold nanocatalyst under different initial pH conditions in example 5 of the present invention for TC. As can be seen from fig. 20, when the initial pH of TC is 3, 5, 6, 7, and 9, the degradation efficiency of TC reaches 80.77%, 84.72%, 88.34%, 80.04%, and 70.60%, respectively, which indicates that the ferrimanganite-gold nanocatalyst in the method of the present invention has a higher catalytic efficiency for degradation of TC when the pH is 3 to 7. Although the catalytic efficiency is reduced to some extent under the alkaline condition, 70.60% of TC is degraded when the pH is 9, which shows that the pH applicability of the iron-manganese ferrite-gold nano catalyst to the degradation of TC in the method is wide, and the method is beneficial to practical application.
Example 6
A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, in particular to a method for treating Tetracycline (TC) in a water body by using the ferromanganese ferrite-gold nano catalyst, which comprises the following steps:
preparation of 100mL,TC solutions with concentrations of 10mg/L, 20mg/L, 30mg/L and 40mg/L respectively (the pH values of the solutions are all 6.0); 10mg of the iron-manganese-oxide-gold nano-catalyst (MFO-Au) prepared in example 1 was taken(3)) Adding into the TC solutions with different concentrations, stirring under ultrasound (at 400-600 r/min, such as 500r/min) in dark for 30min to reach adsorption balance, irradiating with visible light, and adding 5mL of 1M H2O2And (3) fully mixing the solutions, and carrying out a photo-Fenton oxidative degradation reaction for 90min to finish degradation treatment on TC with different concentrations.
Fig. 21 is a graph showing degradation of different concentrations of TC by the ferrite-gold nanocatalyst in example 6 of the present invention. As can be seen from FIG. 21, as the concentration of TC increases from 10mg/L to 40mg/L, the degradation efficiency of TC decreases from 91% to 68%, since as the concentration of TC increases, more TC competes for the active sites of the catalyst and the catalytic sites saturate; meanwhile, TC can generate a plurality of intermediates in the degradation process, and the generated intermediates can compete with TC for active sites of the catalyst, so that the catalytic efficiency is reduced.
Example 7
A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst, in particular to a method for treating Tetracycline (TC) in a water body by using the ferromanganese ferrite-gold nano catalyst, which comprises the following steps:
(1) tap water, river water and lake water are respectively filtered by filter membranes with the particle size of 0.45 mu m, and whether TC is contained in the water body is determined. The filtered water is used as a solvent, a standard addition method is adopted to prepare 20mg/L TC solution, and the TC solutions corresponding to tap water, river water and lake water are sequentially marked as 1-3.
(2) 3 parts of the iron-manganese-oxide-gold nano-catalyst (MFO-Au) prepared in example 1 were taken(3)) 10mg of each part is respectively added into TC solutions (the volume of the solutions is 100mL and the pH value is 6.0) of different water bodies prepared in the step (1), stirring (the rotating speed can be 400 r/min-600 r/min, such as 500r/min) is carried out for 30min to achieve adsorption balance, visible light is adopted for irradiation after the adsorption balance is achieved, and 5mL of H with the concentration of 1M is respectively added2O2And after fully mixing, carrying out the photo-Fenton oxidative degradation reaction for 90min to finish the degradation treatment of TC in different water samples.
Fig. 22 is a graph showing degradation of the iron-manganese ferrite-gold nano-catalyst in different water bodies in example 7 of the present invention. As can be seen from fig. 22, the catalytic reduction time is different when the ferromanganese ferrite-gold nano-catalyst of the present invention is used to treat TCs in different water bodies, but the ferromanganese ferrite-gold nano-catalyst of the present invention can effectively degrade the TCs in each water body in a shorter time, which indicates that the ferromanganese ferrite-gold nano-catalyst prepared by the present invention has a better reduction effect on the TCs in an actual water sample, shows a stronger catalytic activity in practical applications, and can be widely applied to treatment of tetracycline antibiotics in actual water bodies. Meanwhile, the catalytic reduction reaction of the iron-manganese ferrite-gold nano-catalyst to TC in different water bodies conforms to first-order kinetics, and corresponding kinetic constants in different water bodies (distilled water, tap water, river water and lake water) are respectively as follows: kDistilled water＝1.0457min-1、KTap water＝0.7264min-1、KLake water＝0.8210min-1、KRiver water＝0.5863min-1。
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (7)
1. A method for treating organic pollutants by using a ferromanganese ferrite-gold nano catalyst is characterized in that the method is to treat the organic pollutants by using the ferromanganese ferrite-gold nano catalyst; the iron-manganese ferrite-gold nano catalyst comprises iron-manganese ferrite, nano gold particles and negative-valence gold ions, wherein the nano gold particles and the negative-valence gold ions are jointly deposited on the surface of the iron-manganese ferrite; the organic contaminant is an antibiotic; the antibiotic is a tetracycline antibiotic; the tetracycline antibiotic is at least one of tetracycline, oxytetracycline and chlortetracycline;
the preparation method of the iron-manganese ferrite-gold nano catalyst comprises the following steps:
s1, mixing ferrite with ultrapure water, performing ultrasonic treatment, and adding Au3+Stirring the solution to obtain the iron manganese ferrite-Au3+A dispersion liquid; the ratio of the ferrite to the ultrapure water is 400 mg: 40-60 mL; the ferrite and Au3+The ratio of the solution is 400 mg: 1 mL-5 mL; the Au layer3+The solution is chloroauric acid solution; the Au layer3+The concentration of the solution is 10 g/L; the ultrasound is carried out at the temperature of 5-40 ℃; the ultrasonic time is 30-60 min; the rotating speed of the stirring is 400 r/min-600 r/min; the stirring time is 15 min;
s2, and mixing the ferrite-Au obtained in the step S13+The dispersion liquid is put under the condition of illumination for reduction reaction, and N is introduced2Removing O in solution2Meanwhile, adding a sacrificial agent, continuing to react, filtering, cleaning and drying to obtain the ferrite-gold nano catalyst; after the reduction reaction is carried out for 1h, N is introduced2(ii) a Said N is2Continuously introducing for 15-20 min; the iron manganese ferrite-Au3+The volume ratio of the dispersion liquid to the sacrificial agent is 41-65: 20-30; the sacrificial agent is at least one of methanol, formic acid, ammonium oxalate and ethanol; after the sacrificial agent is added, the reaction is continued for 2 to 3 hours; the reduction reaction is carried out under the stirring condition with the rotating speed of 400 r/min-1500 r/min;
the preparation method of the ferrite comprises the following steps:
(1) mixing Fe3+Solution with Mn2+Mixing the solution and stirring to obtain Fe3+And Mn2+The mixed solution of (1);
(2) adjusting the Fe obtained in step (1)3+And Mn2+The pH value of the mixed solution is alkaline, water is added for dilution, the mixed solution is placed in a reaction kettle for reaction, and the ferric manganese ferrite is obtained after washing and drying.
2. The method according to claim 1, wherein the total content of nano-gold particles and negative gold ions in the ferromanganese ferrite-gold nano-catalyst is 1.15-3.92 wt%; the ferrite is nano-particles with the particle size of 20 nm-100 nm.
3. The method according to claim 1, wherein in step (1), the Fe3+And Mn2+Fe in the mixed solution of3+、Mn2+The molar ratio of (A) to (B) is 2: 1; the rotating speed of the stirring is 400 r/min-600 r/min; the stirring time is 10min to 30 min;
in the step (2), NaOH solution is adopted to adjust Fe under the stirring condition3+And Mn2+The pH value of the mixed solution is 11-12; the addition amount of the water is 20 mL-40 mL; the rotating speed of the stirring is 400 r/min-600 r/min; the reaction is carried out at the temperature of 170-190 ℃; the reaction time is 9-11 h.
4. The method according to any one of claims 1 to 3, wherein organic pollutants in the water body are treated by using the iron-manganese ferrite-gold nano-catalyst, and the method comprises the following steps: mixing the iron-manganese ferrite-gold nano catalyst with water containing organic pollutants by ultrasound, stirring, adding a hydrogen peroxide solution for a photo-Fenton oxidation degradation reaction, and finishing the treatment of the organic pollutants in the water.
5. The method according to claim 4, wherein the initial mass ratio of the iron-manganese ferrite-gold nano catalyst to the organic pollutants in the system of the photo-Fenton oxidative degradation reaction is 2.5-10: 1, and H is H2O2The initial ratio of the organic pollutants is 1 mmol-8 mmol: 1 mg-4 mg.
6. The method according to claim 5, wherein the concentration of the organic pollutants in the water body containing the organic pollutants is 10mg/L to 40 mg/L; the pH value of the water body containing the organic pollutants is 3-9.
7. The method according to claim 6, wherein the stirring is performed under dark conditions; the stirring time is 20 min-60 min; the photo-Fenton oxidation degradation reaction is carried out under the illumination condition with the wavelength of 300 nm-800 nm; the rotating speed is controlled to be 300 r/min-900 r/min in the photo-Fenton oxidation degradation reaction process; the time of the photo-Fenton oxidative degradation reaction is 30-120 min.
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