CN110252316B - Hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton-like catalyst and preparation method and application thereof - Google Patents
Hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton-like catalyst and preparation method and application thereof Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
The invention discloses a hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst, and a preparation method and application thereof. The preparation method of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst comprises the steps of firstly preparing porous cerium dioxide nano microspheres by using saccharomyces cerevisiae as a biological template in a high-temperature environment, and then loading the porous cerium dioxide nano microspheres on the surface of ferrihydrite in an in-situ deposition mode. The mesoporous cerium dioxide nano-microspheres in the catalyst have a photosensitive effect, can respond to visible light to generate photon-generated carriers, and promote the activation efficiency of ferrihydrite on hydrogen peroxide in a Fenton system. The generated active free radicals have broad-spectrum catalytic degradation effect on pollutants and have certain practical application value.
Description
Technical Field
The invention belongs to the field of multiphase Fenton-like material preparation and environmental water treatment, and particularly relates to a hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton-like catalyst, and a preparation method and application thereof.
Background
Recently, the enrichment of new contaminants, such as antibiotics, in surface water has led to the evolution of drug-resistant strains and environmental pollution. It is reported that tetracycline, one of the four major classes of antibiotics, ranks the annual yield of the antibiotic class first in china. And because the aromatic structure and the functional group are stable, the natural degradation in the environment is difficult. The traditional physical treatment method can not degrade the novel pollutants, so the advanced oxidation technology, especially hydrogen peroxide (H)2O2) Fenton's technology as an oxidizing agent is of interest and has been applied to the degradation of this new class of contaminant antibiotics.
The traditional homogeneous Fenton oxidation technology mainly uses Fe2+And H2O2Under acidic conditions, the reaction generates hydroxyl free radicals (. OH) which can attack organic pollutants, so that the pollutants are gradually degraded and even mineralized into H2O and CO2The process of (1). However, the practical application of the conventional homogeneous fenton oxidation is limited by several aspects, including: (1) OH production is limited by pH, and generally only occurs in the pH range of 2.5 to 3.5; (2) fe in the system2+The regeneration rate of the catalyst is extremely low, so that the yield of OH is not high, and the reaction activity is limited; (3) iron hydroxide sludge precipitation is easily generated in the reaction process, and new chromaticity and impurity pollution are generated to water quality while organic pollution is degraded.
In order to overcome the defects of the traditional homogeneous fenton, the iron-based heterogeneous fenton catalyst is produced, wherein natural iron mineral ferrihydrite widely existing in the nature is paid extensive research attention by the unique catalytic and adsorption properties of the ferrihydrite. In particular, it can be used as Fenton-like catalyst in high-grade oxidation system to activate H2O2Produce OH and do not selectively attackOrganic molecules degrade it. But ferrihydrite alone is not as catalytically active against contaminants in fenton-like systems. Therefore, the novel efficient Fenton-like catalytic composite material is constructed by using the ferrihydrite as a carrier, and the important significance is achieved for effectively improving the catalytic activity of the iron-based Fenton-like material.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst. The method comprises the steps of synthesizing hollow cerium dioxide nano microspheres by using yeast as a biological template, and loading the hollow cerium dioxide nano microspheres on the surface of ferrihydrite by a precipitation method.
The method effectively utilizes cheap and abundant Saccharomyces cerevisiae microorganisms, has multiple active sites, has photosensitive response, and can effectively activate H2O2Iron-based cerium-based efficient Fenton-like composite material (hCeO)2/fh)。
The invention also aims to provide the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst prepared by the method.
The invention further aims to provide application of the hollow cerium dioxide microsphere-supported ferrihydrite heterogeneous fenton-like catalyst, in particular application of the hollow cerium dioxide microsphere-supported ferrihydrite heterogeneous fenton-like catalyst in a low-energy-consumption visible light source/fenton system for degrading organic pollutants.
The purpose of the invention is realized by the following technical scheme:
hollow cerium dioxide microsphere loaded ferrihydrite (hCeO)2/fh) preparation method of the heterogeneous Fenton-like catalyst, comprising the following steps:
(1) adding yeast and a cerium dioxide precursor into water, uniformly mixing, adding an alkaline substance to obtain a mixed solution, standing, aging, washing, drying, calcining at 500-700 ℃ for 1-3 h, and cooling to obtain hollow cerium dioxide nano microspheres;
(2) adding hollow cerium dioxide nano microspheres into water, then adding ferrihydrite precursor and alkaline substance to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, reacting for 2-4 h at room temperature, centrifuging, washingWashing and drying to obtain hCeO2A/fh heterogeneous Fenton-like catalyst;
the mass ratio of the hollow cerium dioxide nano microspheres to the ferrihydrite precursor is (0.2-1): 18.16.
the yeast in the step (1) is preferably Saccharomyces Cerevisiae (Saccharomyces Cerevisiae).
The yeast in the step (1) is preferably added in a form of yeast freeze-dried powder, and the mass ratio of the yeast freeze-dried powder to the cerium dioxide precursor is preferably 0.8-1.2: 1.
The ceria precursor in step (1) is preferably Ce (NO)3)3·6H2O; the mass ratio of the ceria precursor to water is preferably 1: (20-30).
The concentration of the alkaline substance in the mixed solution in the step (1) is preferably 6-8 g/L.
The alkaline substance in the step (1) is preferably NaOH, the alkaline substance is preferably added in the form of an aqueous solution, and the mass concentration of the aqueous solution is preferably 0.05-0.1 g/ml.
The mixing in the step (1) is preferably ultrasonic mixing, and the ultrasonic mixing time is preferably 60-90 min.
The standing and aging time in the step (1) is preferably 12-14 h.
After the alkaline substance is added in the step (1), oscillation treatment is carried out, wherein the oscillation speed is preferably 160-180 rpm, and the time is 60-90 min; the washing is preferably carried out for 1-3 times by respectively using ethanol and water; the drying condition is preferably vacuum drying for 6-16 h at 50-100 ℃.
The calcination in the step (1) is preferably carried out in a muffle furnace, and the temperature is increased to 600 ℃ at a temperature increase rate of 1 ℃/min.
The mass ratio of the hollow cerium dioxide nano microspheres in the step (2) to water is preferably (0.2-1): 240.
the ferrihydrite precursor in the step (2) is preferably Fe (NO)3)3·9H2O。
The ferrihydrite precursor and the alkaline substance in the step (2) are preferably added in the form of aqueous solutions thereof, wherein the mass ratio of the solute to the solvent in the ferrihydrite precursor aqueous solution is preferably 0.227: (1-1.2), the mass concentration of the alkaline substance aqueous solution is preferably 0.05-0.1 g/ml.
The ferrihydrite precursor aqueous solution and the alkaline substance aqueous solution are preferably added simultaneously in a dropwise manner and are added within 5-10 min. The stirring speed of the dropwise addition is 160-180 rpm.
The concentration of the alkaline substance in the mixed solution in the step (2) is preferably 12-14 g/L. The alkaline substance is preferably NaOH.
The oscillation rate of the reaction in the step (2) is preferably 160-180 rmp.
The centrifugation condition in the step (2) is preferably 6000 to 8000rpm for 10 to 15 min; the washing condition is preferably that the product is respectively dispersed in ethanol and water and centrifuged, and the centrifugation is repeated for 1-3 times, wherein the centrifugation condition is preferably that the product is centrifuged at 6000-8000 rpm for 10-15 min; the drying is preferably freeze drying, and the drying is preferably carried out for 24-36 hours at-50 ℃.
The hollow cerium dioxide microspheres prepared by the method load the ferrihydrite heterogeneous Fenton-like catalyst.
The hCeO2In the/fh multiphase Fenton-like catalyst, the mass ratio of the hollow cerium dioxide nano microspheres to the ferrihydrite is (0.05-0.25): 1.
the hollow cerium dioxide microspheres load the ferrihydrite multiphase Fenton-like catalyst, ferrihydrite is used as a carrier and is in an amorphous shape, and the hollow cerium dioxide is in a hollow porous microspherical shape and is tightly embedded into the surface of the ferrihydrite.
The hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst is applied to the field of photo-Fenton degradation of organic matters.
The application is preferably the removal of organic matter from wastewater.
The method for removing the organic matters in the wastewater comprises the following steps: mixing hCeO2Mixing the/fh multiphase Fenton-like catalyst with the wastewater uniformly, oscillating and adsorbing the mixture under the condition of keeping out of the sun, adding H after the adsorption balance is achieved2O2And performing photo-Fenton catalytic degradation under a visible light source to finish degradation treatment on organic matters in the wastewater.
The hCeO2The addition amount of the/fh multiphase Fenton-like catalyst in the wastewater is preferably 0.2-1.2 g/L; said H2O2The concentration in the wastewater is preferably 20 to 100 mmol/L.
The concentration of the organic matters in the wastewater is preferably 10-30 mg/L; more preferably 10 to 20 mg/L.
The organic matter is preferably at least one of antibiotic, tetrabromobisphenol A (TBBPA), rhodamine B (RhB) and 2, 4-dichlorophenol (2, 4-DCP); the antibiotic is preferably Tetracycline (TC).
The photo-Fenton catalytic degradation of tetrabromobisphenol A, rhodamine B and 2, 4-dichlorophenol is preferably carried out under the condition of the pH of the wastewater (wherein the pH of the wastewater containing tetrabromobisphenol A is about 6.43, the pH of the wastewater containing rhodamine B is about 5.62 and the pH of the wastewater containing 2, 4-dichlorophenol is about 7.76); the photo-Fenton catalytic degradation of the antibiotic is preferably carried out at a pH of the wastewater of 4.0.
The photo-Fenton catalytic degradation is preferably carried out under the condition of low-energy-consumption LED lamp illumination with the power of 5W.
The time of the photo-Fenton catalytic degradation is preferably 10-120 min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a hollow cerium dioxide microsphere loaded ferrihydrite (hCeO)2/fh) the heterogeneous Fenton-like catalyst consists of hollow cerium dioxide nano microspheres and ferrihydrite, wherein the hollow cerium dioxide nano microspheres are porous and are tightly embedded into the surface of amorphous ferrihydrite. Ferrihydrite itself acts as an iron-based compound, and its surface contains abundant Fe3+And hydroxyl radicals, for which H deactivates as Fenton-like catalysts2O2Providing the potential. The hollow cerium dioxide is used as a semiconductor, can generate a photon-generated carrier under the condition of a visible light source, and the photon-generated carrier is transferred to the surface of the ferrihydrite in close contact with the semiconductor, so that the ferrihydrite can be effectively promoted to H in a Fenton system2O2Thereby increasing the yield of active groups and the efficiency of contaminant degradation. The hollow cerium dioxide microsphere load of the inventionThe ferrihydrite multiphase Fenton catalyst can degrade different types of organic pollutants, has the characteristics of high degradation rate, high removal efficiency, simple and convenient operation and low cost, does not produce any secondary pollution, and has environmental protection benefit.
2. The method effectively utilizes the saccharomyces cerevisiae of the waste microbial biomass as the biological template and gasifies the saccharomyces cerevisiae into CO in a high-temperature environment2Thereby promoting the cerium dioxide to form the nano-microsphere with a porous structure, and being beneficial to the absorption of visible light and the transfer effect of photon-generated carriers. The cerium dioxide nano-microspheres are loaded on the surface of the ferrihydrite, so that the surface of the ferrihydrite also presents rugged porous shape, and simultaneously, the mass transfer diffusion of pollutants on the surface of the composite material and the contact action of the pollutants and active groups are facilitated.
3. The hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst is prepared by adopting a simple high-temperature calcination method and an in-situ precipitation method, the reaction condition is easy to regulate and control, the operation is simple and convenient, no secondary pollution is generated in the preparation process, and the hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst has the advantages of environmental friendliness and the like.
4. The hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst prepared by the invention can generate photoproduction holes and photoproduction electrons under the condition of low-energy-consumption LED visible light illumination, and further transmits the photoproduction holes and the photoproduction electrons to the surface of ferrihydrite, so that the catalytic application of iron elements in ferrihydrite in a fenton-like system is expanded, typical environmental pollution antibiotic wastewater and other typical organic pollution wastewater (fire retardant, dye and phenol) are effectively treated, and the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst has the characteristics of simplicity and convenience in operation, low cost, excellent degradation performance, rapidness in treatment and the; the maximum degradation efficiency of tetracycline is 99.7%, the mineralization rate is 71.2%, the maximum degradation efficiency of tetrabromobisphenol A is 100%, the maximum degradation efficiency of rhodamine B is 85.2%, the maximum degradation efficiency of 2, 4-dichlorophenol is 81.8%, and good stability is shown. Thus, the hCeO of the present invention2The/fh multiphase Fenton catalyst can be widely applied to purification and harmless treatment of organic polluted wastewater, and has important significance for developing microbial template supported catalysts, iron-based multiphase Fenton catalysts and environmental pollutant treatment.
Drawings
FIG. 1 shows a hollow cerium dioxide microsphere loaded ferrihydrite heterogeneous Fenton-like catalyst (5-hCeO) prepared in example 1 of the present invention2/fh、15-hCeO2/fh、25-hCeO2/fh), pure ferrihydrite (fh) prepared in comparative example 1, and hollow cerium oxide nano-microspheres (hCeO) prepared in example 12) X-ray diffraction pattern of (a).
FIG. 2 shows a hollow cerium dioxide microsphere loaded ferrihydrite heterogeneous Fenton-like catalyst (25-hCeO) prepared in example 1 of the present invention2/fh) at a magnification of 4000 times.
FIG. 3 shows the hollow cerium oxide microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 12/fh) of the X-ray photoelectron full spectrum.
FIG. 4 shows the hollow cerium dioxide microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (5-hCeO) prepared in example 1 of the present invention2/fh、15-hCeO2/fh、25-hCeO2/fh), pure ferrihydrite (fh) prepared in comparative example 1, and hollow cerium oxide nano-microspheres (hCeO) prepared in example 12) The ultraviolet-visible light diffuse reflection absorption spectrogram.
FIG. 5 shows the hollow cerium dioxide microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (5-hCeO) prepared in example 1 of the present invention2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/fh、25-hCeO2/fh) and pure ferrihydrite (fh) prepared in comparative example 1 were shown to have a degrading effect on tetracycline in a photo-fenton system.
FIG. 6 shows different amounts of ceria microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO in example 1)2/fh) photo-Fenton catalytic degradation profile of tetracycline.
FIG. 7 shows the ceria microspheres loaded ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 12/fh) light-Fenton catalytic degradation curve of tetracycline under different hydrogen peroxide concentrations.
FIG. 8 shows the ceria microspheres loaded ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 12/fh) at different pGraph of tetracycline degradation under H in light-Fenton system.
FIG. 9 shows the ceria microspheres loaded ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 12/fh) graph of the photo-Fenton catalytic degradation effect on different types of organic pollutants.
FIG. 10 shows a ceria microsphere loaded ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 1 of the present invention2Fh) and the pure ferrihydrite prepared in the comparative example 1 are used for plotting the mineralization rate of the tetracycline in the photo-fenton catalytic degradation process.
Detailed Description
The invention is described in further detail below with reference to specific examples and the accompanying drawings of the specification, without thereby limiting the embodiments of the invention.
The Saccharomyces Cerevisiae (Saccharomyces Cerevisiae) used in the embodiment of the invention is purchased from China general microbiological culture collection center with the preservation number of CGMCC 2.3849.
Example 1
A hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst is prepared by the following steps:
(1) collecting 1g Saccharomyces cerevisiae dry powder and 1g Ce (NO)3)3·6H2And O, dissolving in 20mL of deionized water, and performing ultrasonic treatment for 60min at room temperature to obtain a mixed solution. To the mixture was added dropwise 10mL of an aqueous NaOH solution (containing 0.2g of NaOH) and the mixture was shaken at 160rpm at room temperature for 1 hour, allowed to stand at room temperature for 12 hours, and then centrifuged to collect the mixture, which was washed with ethanol 1 time and deionized water 2 times. Vacuum drying the obtained precipitate at 80 deg.C for 6h, taking out, placing into a muffle furnace, heating to 600 deg.C at a rate of 1 deg.C/min, calcining at 600 deg.C for 2h, naturally cooling to obtain hollow cerium dioxide nanometer microsphere (hCeO)2)。
(2) 0.025g, 0.05g, 0.075g, 0.1g and 0.125g of the hollow cerium dioxide nano-microspheres prepared in the step (1) are respectively dissolved in 30mL of deionized water, and are defined as A solution. 2.27g of Fe (NO)3)3·9H2The O particles were dissolved in 10mL of deionized water,defined as solution B. 0.674g of NaOH pellets were dissolved in 10mL of deionized water, defined as solution C. The solution B and the solution C are added to the solution A at 160rpm, simultaneously and dropwise, within 5min, and the pH of the mixed solution is adjusted to 7.0+ _0.1 at room temperature, and then the reaction is carried out for 3h under shaking at 160rpm and room temperature. Then centrifugally separating at 4000rpm, washing for 2 times by using deionized water, collecting precipitate, and freeze-drying at-50 ℃ for 12 hours to obtain the hollow cerium dioxide microsphere loaded ferrihydrite (hCeO)2Fh) heterogeneous Fenton-like catalyst, and the products are respectively marked as 5-hCeO according to the adding amount of 0.025g, 0.05g, 0.075g, 0.1g and 0.125g of hollow cerium dioxide nano microspheres2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2Fh and 25-hCeO2/fh。
Comparative example 1
A production of pure iron ore (fh), comprising the steps of:
2.27g Fe (NO)3)3·9H2O was dissolved in 10mL of deionized water, defined as solution B, and 0.674g of NaOH pellets were dissolved in 10mL of deionized water, defined as solution C. The solution C was added dropwise to the solution B, and the pH of the mixed solution was adjusted to 7.0+ _0.1 at room temperature, followed by shaking at 160rpm at room temperature for 3 hours. Centrifuging at 4000rpm, collecting precipitate, and freeze drying at-50 deg.C for 12 hr to obtain pure iron ore (fh) material.
The hollow cerium dioxide microspheres prepared in example 1 of the present invention were loaded with ferrihydrite heterogeneous fenton-like catalyst (5-hCeO)2/fh、15-hCeO2/fh、25-hCeO2/fh) and hollow cerium dioxide nano-microspheres (hCeO)2) And the X-ray diffraction characterization analysis was performed on the pure ferrihydrite (fh) material prepared in comparative example 1, the results are shown in FIG. 1, hCeO2Diffraction peaks appear at positions of 28.6 °, 33.2 °, 47.8 °, 56.3 °, 58.7 °, 69.4 °, 76.7 °, and 88.4 °, respectively, corresponding to (111), (200), (220), (311), (222), (400), (331), and (422) crystal planes in the ceria fluorite structure (JCPDS No. 50-1275). And diffraction peaks were observed at diffraction angles of around 35 DEG and 63 DEG for fhThis is consistent with the two broad reflection peaks of ferrihydrite. The ceria microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (5-hCeO) in three different proportions2/fh、15-hCeO2/fh、25-hCeO2/fh), all contain hCeO2And diffraction peaks of fh, which indicates hCeO2Successfully loaded on ferrihydrite and hCeO2The incorporation of (b) had no effect on fh structure formation.
The hollow cerium dioxide microspheres prepared in the example 1 of the invention load ferrihydrite (25-hCeO)2/fh) the results of the scanning electron microscopy analysis of the heterogeneous Fenton-like catalyst are shown in FIG. 2. As can be seen from FIG. 2, the hollow cerium dioxide microspheres prepared by the invention load ferrihydrite (25-hCeO)2/fh) heterogeneous Fenton-like catalyst, the surface of which shows a non-uniform rough state accompanied by many voids, which indicates that hCeO has a large pore structure2Successfully loaded on the fh surface to ensure that the surface of the fh surface is rough and porous, 25-hCeO2The analysis result of the scanning electron microscope of/fh is consistent with the characterization and analysis result of X-ray diffraction.
The hollow cerium dioxide microspheres prepared in the embodiment 1 of the invention are loaded with ferrihydrite (15-hCeO)2/fh) the heterogeneous Fenton-like catalyst was subjected to X-ray photoelectron spectroscopy, and the results are shown in FIG. 3. As can be seen from FIG. 3, the hollow cerium dioxide microspheres prepared by the invention load ferrihydrite (15-hCeO)2And/fh) the four elements of C, Fe, O and Ce in the heterogeneous Fenton-like catalyst have no other impurity peaks except the four elements, which indicates that no impurity is doped. The Fe region can be divided into two characteristic peaks of Fe 2p1/2 and Fe 2p 3/2. The above results all show that 15-hCeO2The/fh heterogeneous Fenton-like catalyst is successfully synthesized.
The hollow cerium dioxide microspheres prepared in example 1 of the present invention were loaded with ferrihydrite heterogeneous fenton-like catalyst (5-hCeO)2/fh，15-hCeO2/fh，25-hCeO2/fh) and hollow cerium dioxide nano-microspheres (hCeO)2) And ultraviolet-visible light diffuse reflection absorption spectrum analysis was performed on the pure iron ore (fh) material prepared in comparative example 1, and the results are shown in fig. 4. As shown in FIG. 4, the hollow cerium dioxide nanospheres (hCeO)2) In the ultraviolet and visibleThe region showed greater light absorption with a sharp decrease in absorbance at 470 nm. And pure iron ore shows obvious adsorption capacity in the whole spectrum area. Compared with fh, the hollow cerium dioxide microspheres load ferrihydrite multiphase Fenton-like catalyst (5-hCeO)2/fh，15-hCeO2/fh，25-hCeO2/fh) has increased light absorption intensity in the visible light region, wherein the light absorption intensity is 15-hCeO2The/fh shows the best red shift in all samples, and the hollow cerium dioxide nano microspheres loaded in the minerals can promote the absorption of solar energy.
Example 2
Investigating different hCeO2The influence of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst with the doping amount on the photo-Fenton catalytic degradation of the antibiotic tetracycline wastewater.
The hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst prepared in the embodiment 1 of the invention and the pure ferrihydrite (fh) material prepared in the proportion 1 are applied to tetracycline wastewater photo-fenton catalytic degradation treatment, and the steps are as follows: the tetracycline stock solution was diluted to 20mg/L with deionized water and 1.0mol/L H2SO4And NaOH solution to adjust the initial pH value of the tetracycline solution to 4.0. 20mg of 5-hCeO of example 1 were weighed out separately2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/fh、25-hCeO2The/fh heterogeneous Fenton-like catalyst and fh in the comparative example 1 are added into a tetracycline simulation waste water solution with the volume of 50mL and the concentration of 20mg/L, the tetracycline simulation waste water solution is oscillated for 1h under the dark condition to reach the adsorption equilibrium, a certain amount of hydrogen peroxide is added to ensure that the final concentration of the hydrogen peroxide in the tetracycline simulation waste water solution is 50mmol/L, an LED lamp is turned on, and the tetracycline simulation waste water solution is irradiated under the visible light condition (lambda)>420nm) is subjected to light-Fenton catalytic degradation reaction, the reaction time is 60min, samples are respectively sampled at 2min, 5min, 10min, 20min, 40min and 60min during the reaction process, solid-liquid separation is carried out through a 0.22 mu m filter membrane, the concentration of the residual antibiotic tetracycline in the filtrate is measured at 357nm by using an ultraviolet spectrophotometer, and the residual rate of the tetracycline is calculated. In this example, 1 tetracycline solution (containing no catalyst, 50mL in volume, and 20mg/L in concentration) was setConcentration of hydrogen oxide was 50mmol/L) was used as a control group, and the residual rate of tetracycline was measured and calculated under the same conditions for blank comparison. Different hCeO2The degradation curve of the doping ratio loaded water-body ore multiphase Fenton-like catalyst to tetracycline in a photo-Fenton system is shown in FIG. 5. As can be seen from FIG. 5, the degradation rate of tetracycline is very low under the conditions of only visible light and hydrogen peroxide, and only weak degradation reaction occurs. The degradation of pure fh to tetracycline still remained 50.83% in the system after 60min, with a degradation efficiency of 49.17%. By using 5-hCeO2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/fh、25-hCeO2After the/fh heterogeneous Fenton-like catalyst degrades tetracycline in a photo-Fenton system for 60min, the residual rates of the tetracycline in the system are respectively 35.62%, 20.2%, 7.39%, 9.78% and 12.36%; the corresponding tetracycline degradation rates were 64.38%, 79.80%, 92.61%, 90.22, and 87.64%, respectively. The doping of the hollow cerium dioxide nano microspheres can effectively promote the degradation of ferrihydrite materials to the antibiotic pollution in a photo-Fenton system.
Example 3
The influence of the dosage of the heterogeneous Fenton-like catalyst of the iron pyrite loaded by different hollow cerium dioxide microspheres on the photo-Fenton catalytic degradation of the tetracycline wastewater of the antibiotic is examined.
The hollow cerium dioxide microspheres prepared in the embodiment 1 of the invention are loaded with ferrihydrite heterogeneous fenton-like catalyst (15-hCeO)2/fh) is applied to the light-Fenton catalytic degradation treatment of tetracycline wastewater, and the steps are as follows: the tetracycline stock solution was diluted to 20mg/L with deionized water and 1.0mol/L H2SO4And NaOH solution to adjust the initial pH value of the tetracycline solution to 4.0. 10mg, 20mg, 40mg and 60mg of the 15-hCeO of example 1 were weighed out separately2Adding the/fh heterogeneous Fenton-like catalyst into a tetracycline simulation waste water solution with the volume of 50mL and the concentration of 20mg/L, oscillating for 1h under the condition of keeping out of the light to enable the tetracycline simulation waste water solution to reach adsorption equilibrium, adding a certain amount of hydrogen peroxide to enable the final concentration of the hydrogen peroxide in the tetracycline simulation waste water solution to be 50mmol/L, turning on an LED lamp, and irradiating under the condition of light (lambda)>420nm) is subjected to photo-Fenton catalytic degradation reaction, and the reaction time is 60miAnd n, sampling at 2min, 5min, 10min, 20min, 40min and 60min in the reaction process, performing solid-liquid separation by using a 0.22 mu m filter membrane, measuring the concentration of the residual antibiotic tetracycline in the filtrate at 357nm by using an ultraviolet spectrophotometer, and calculating the residual rate of the tetracycline. 15-hCeO with different catalyst dosage2The tetracycline degradation profile of the/fh heterogeneous Fenton-like catalyst is shown in FIG. 6. As can be seen from FIG. 6, 0.2g/L, 0.4g/L, 0.8g/L and 1.2g/L of 15-hCeO were used2After the/fh heterogeneous Fenton-like catalyst degrades tetracycline in a photo-Fenton system for 60min, the residual rates of the tetracycline in the system are respectively 15.06%, 7.39%, 2.93% and 1.25%; the corresponding tetracycline degradation rates were 84.94%, 92.61%, 97.17% and 98.75%, respectively. The degradation rate of tetracycline increases with increasing catalyst dosage, generally speaking, the more catalysts, the H2O2The more active sites are decomposed, thereby promoting the degradation of organic substances.
Example 4
And (3) investigating the influence of different hydrogen peroxide concentrations on the photo-Fenton catalytic degradation of the antibiotic tetracycline by the hollow cerium dioxide microsphere loaded ferrihydrite heterogeneous Fenton catalyst.
The hollow cerium dioxide microspheres prepared in the embodiment 1 of the invention are loaded with ferrihydrite heterogeneous fenton-like catalyst (15-hCeO)2/fh) is applied to the light-Fenton catalytic degradation treatment of tetracycline wastewater, and the steps are as follows: the tetracycline stock solution was diluted to 20mg/L with deionized water and 1.0mol/L H2SO4And NaOH solution to adjust the initial pH value of the tetracycline solution to 4.0. 20mg of 15-hCeO from example 1 were taken2Adding/fh heterogeneous Fenton-like catalyst into a tetracycline simulation waste water solution with the volume of 50mL and the concentration of 20mg/L, oscillating for 1h under the condition of keeping out of the light to enable the tetracycline simulation waste water solution to reach adsorption equilibrium, adding a certain amount of hydrogen peroxide to enable the final concentration of the hydrogen peroxide in the tetracycline simulation waste water solution to be 20mmol/L, 50mmol/L, 100mmol/L and 150mmol/L, turning on an LED lamp, and irradiating under the condition of light (lambda)>420nm) is subjected to photo-Fenton catalytic degradation reaction, the reaction time is 60min, samples are respectively sampled for 2min, 5min, 10min, 20min, 40min and 60min in the reaction process, the solid and liquid are separated by a 0.22 mu m filter membrane, and ultraviolet light is utilized for light splittingThe concentration of the antibiotic tetracycline remained in the filtrate was measured by a photometer at 357nm, and the tetracycline residue was calculated. 15-hCeO under different hydrogen peroxide concentration conditions2The tetracycline degradation profile of the/fh heterogeneous Fenton-like catalyst is shown in FIG. 7. As can be seen from FIG. 7, tetracycline-simulated wastewater solutions having hydrogen peroxide concentrations of 20mmol/L, 50mmol/L, 100mmol/L and 150mmol/L, respectively, were subjected to 15-hCeO2After 60min of the/fh light-Fenton catalytic degradation, the residual rates of tetracycline in the system are respectively 12.64%, 7.39%, 6.59% and 8.68%. The corresponding tetracycline degradation rates were 87.36%, 92.61%, 93.41% and 91.32%, respectively. The degradation rate of the tetracycline is increased and then reduced along with the concentration of the hydrogen peroxide, and the degradation rate of the tetracycline reaches the maximum when the concentration of the hydrogen peroxide is 100 mmol/L. When the concentration of the hydrogen peroxide is more than or less than 100mmol/L, the degradation efficiency of the tetracycline is gradually reduced.
Example 5
The influence of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase Fenton catalyst on the photo-Fenton catalytic degradation of the antibiotic tetracycline wastewater under different pH values is investigated.
The hollow cerium dioxide microspheres prepared in the embodiment 1 of the invention are loaded with ferrihydrite heterogeneous fenton-like catalyst (15-hCeO)2/fh) is applied to the light-Fenton catalytic degradation treatment of tetracycline wastewater, and the steps are as follows: the tetracycline stock solution was diluted to 20mg/L with deionized water and 1.0mol/L H2SO4And NaOH solution to adjust the initial pH of the tetracycline solution to 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, and 9.0. 20mg of 15-hCeO from example 1 were taken2Adding the/fh heterogeneous Fenton-like catalyst into a tetracycline simulation waste water solution with the volume of 50mL and the concentration of 20mg/L, oscillating for 1h under the condition of keeping out of the light to enable the tetracycline simulation waste water solution to reach adsorption equilibrium, adding a certain amount of hydrogen peroxide to enable the final concentration of the hydrogen peroxide in the tetracycline simulation waste water solution to be 50mmol/L, turning on an LED lamp, and irradiating under the condition of light (lambda)>420nm) is subjected to photo-Fenton catalytic degradation reaction, the reaction time is 60min, samples are respectively sampled at 2min, 5min, 10min, 20min, 40min and 60min in the reaction process, solid-liquid separation is carried out through a 0.22 mu m filter membrane, and an ultraviolet spectrophotometer is utilized to measure the residual antibiotic tetracycline in the filtrate at 357nmThe residual rate of tetracycline is calculated. 15-hCeO under different pH conditions2The tetracycline degradation profile of the/fh heterogeneous Fenton-like catalyst is shown in FIG. 8. As can be seen from FIG. 8, 15-hCeO was observed when the pH in the system was 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 and 9.0, respectively2After tetracycline is degraded in the photo-Fenton system for 60min, the tetracycline residue rates in the system are 10.62%, 7.39%, 8.62%, 11.26%, 10.91%, 12.39% and 8.61%, respectively. The corresponding tetracycline degradation efficiencies were 89.38%, 92.61%, 91.38%, 88.74%, 89.09%, 87.61%, and 91.39%, respectively. The results show that the tetracycline degradation rate increases when the solution pH is raised from 3.0 to 4.0, but that the tetracycline degradation efficiency decreases when the pH is further raised to neutral and alkaline.
Example 6
Examination of the hollow cerium oxide microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 1 of the present invention2/fh) efficiency of degradation of different contaminants in photo-fenton system.
The hollow cerium dioxide microspheres prepared in the embodiment 1 of the invention are loaded with ferrihydrite heterogeneous fenton-like catalyst (15-hCeO)2/fh) is applied to the photo-Fenton degradation treatment of wastewater of different organic polluted wastewater, and the steps are as follows: respectively taking 10mg/L of wastewater solutions of rhodamine B, tetrabromobisphenol A, 2, 4-dichlorophenol and 20mg/L of tetracycline, respectively taking 20mg of 15-hCeO in example 1 under the natural pH condition of the wastewater solutions of the rhodamine B, the tetrabromobisphenol A and the 2, 4-dichlorophenol and under the pH condition of the wastewater solutions of the tetracycline being 4.02Adding/fh multiphase Fenton-like catalyst into 50mL of the four solutions, oscillating for 1h under the condition of keeping out of the light, adding a certain amount of hydrogen peroxide to ensure that the final concentration of the hydrogen peroxide in the four waste water solutions is 50mmol/L, turning on an LED lamp, and irradiating under the condition of light (lambda)>420nm) is subjected to photo-Fenton catalytic degradation reaction, the reaction time is 120min, and the samples are respectively sampled and filtered by a 0.22 mu m filter membrane for solid-liquid separation in the reaction processes of 2min, 5min, 10min, 20min, 40min, 90min, 60min and 120 min. Measuring residual rhodamine B and tetracycline in filtrate at 567nm and 357nm respectively by using ultraviolet spectrophotometerConcentration, 2, 4-dichlorophenol and tetrabromobisphenol A wastewater solutions were each detected by High Performance Liquid Chromatography (HPLC) using C18 (150. mu. m.times.4.6. mu.m, 5 μm, Agilent, USA) as a liquid chromatography column under conditions of a detection wavelength of 254nm, a column temperature of 30 ℃ and a mobile phase of methanol: distilled water 60: 40(v/v), the flow rate is 0.8mL/min, and the sample injection amount is 20 mu L; the detection conditions of tetrabromobisphenol A are that the detection wavelength is 209nm, the column temperature is 30 ℃, and the mobile phase is methanol: distilled water 85: 15(v/v), flow rate 1.0mL/min, sample size 20. mu.L. And calculating the residual rate of each organic pollutant. 15-hCeO2The degradation profile of the/fh heterogeneous fenton-like catalyst for different contaminants is shown in fig. 9. As can be seen from FIG. 9, 15-hCeO2After degrading rhodamine B, tetrabromobisphenol A and 2, 4-dichlorophenol for 120min in a light-Fenton system, the residual rates of the rhodamine B, the tetrabromobisphenol A and the 2, 4-dichlorophenol in the system are respectively 12.71 percent, 0 percent and 18.29 percent. The degradation efficiencies of corresponding rhodamine B, tetrabromobisphenol A and 2, 4-dichlorophenol are 87.29%, 100% and 81.71% respectively, and the degradation rate of the tetrabromobisphenol A reaches 100% in 20 min. The result shows that the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst prepared in the embodiment 1 of the invention has broad spectrum for degrading organic pollutants and high degradation efficiency.
Example 7
Examination of the hollow cerium oxide microspheres loaded with ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 1 of the present invention2/fh) and that of pure ferrihydrite (fh) prepared in comparative example 1, on the mineralization rate of tetracycline in the photo-fenton system.
The hollow cerium dioxide microsphere loaded ferrihydrite heterogeneous Fenton-like catalyst (15-hCeO) prepared in example 1 of the invention is explored2Fh) and pure ferrihydrite (fh) prepared in comparative example 1, for tetracycline mineralization by the following procedure: the tetracycline stock solution was diluted to 20mg/L with deionized water and 1.0mol/L H2SO4And adjusting the initial pH value of the tetracycline solution to 4.0 by using a NaOH solution to obtain a tetracycline simulation waste water solution. 20mg of each of the 15-hCeO of example 1 were taken2/fh heterogeneous Fenton-like catalystAnd the pure ferrihydrite (fh) in the comparative example 1 was added to the tetracycline simulated waste water solution having a volume of 50mL and a concentration of 20mg/L, the solution was shaken for 1h under the dark condition to reach adsorption equilibrium, then a certain amount of hydrogen peroxide was added to give a final concentration of 50mmol/L in the tetracycline simulated waste water solution, the LED lamp was turned on, and the solution was irradiated with light (λ)>420nm) is subjected to photo-Fenton catalytic degradation reaction, the reaction time is 60min, samples are respectively sampled for 2min, 5min, 10min, 20min, 40min and 60min in the reaction process, solid-liquid separation is carried out through a 0.22 mu m filter membrane, and the detection is immediately carried out by using a total organic carbon analyzer. 15-hCeO2The tetracycline degradation profile of the/fh heterogeneous fenton-like catalyst and the pure ferrihydrite (fh) material is shown in fig. 10. As can be seen from FIG. 10, 15-hCeO2The mineralization rate of the/fh heterogeneous Fenton-like catalyst to tetracycline is obviously higher than that of pure fh, which shows that the two reaction systems can oxidize the tetracycline into inorganic carbon, and the hCeO2Can further promote mineralization of the target antibiotic.
In conclusion, the invention effectively utilizes the cheap and abundant saccharomyces cerevisiae as the biological template to successfully synthesize the hollow cerium dioxide nano-microspheres with a plurality of active sites, and further loads the hollow cerium dioxide nano-microspheres on the surface of the ferrihydrite by the in-situ hydrothermal method to obtain the newly synthesized hollow cerium dioxide nano-microspheres which have a plurality of active sites, high photosensitive response intensity and can effectively activate H2O2The iron-based cerium-based high-efficiency Fenton-like catalyst. The catalyst has simple preparation process, no secondary pollution and good environmental protection benefit. Can effectively catalyze and degrade organic pollutants such as antibiotics, dyes, flame retardants and the like, has a certain degradation broad spectrum, and has high degradation rate, simple and convenient operation in the degradation process, environmental protection and no secondary pollution. The invention has important significance for developing the high-efficiency Fe-based Fenton heterogeneous catalyst.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst is characterized by comprising the following steps of:
(1) adding yeast and a cerium dioxide precursor into water, uniformly mixing, adding an alkaline substance to obtain a mixed solution, standing, aging, washing, drying, calcining at 500-700 ℃ for 1-3 h, and cooling to obtain hollow cerium dioxide nano microspheres;
(2) adding hollow cerium dioxide nano microspheres into water, then adding ferrihydrite precursor and alkaline substance to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, reacting for 2-4 h at room temperature, centrifuging, washing and drying to obtain hCeO2A/fh heterogeneous Fenton-like catalyst;
the mass ratio of the hollow cerium dioxide nano microspheres to the ferrihydrite precursor in the ferrihydrite precursor solution is (0.2-1): 18.16.
2. the preparation method of the hollow ceria microsphere-supported ferrihydrite multiphase fenton-like catalyst according to claim 1, wherein the yeast in step (1) is saccharomyces cerevisiae; the yeast is added in the form of yeast freeze-dried powder, and the mass ratio of the yeast freeze-dried powder to the ceric oxide precursor is 0.8-1.2: 1.
3. The preparation method of the hollow cerium dioxide microsphere-supported ferrihydrite multiphase fenton-like catalyst according to claim 1 or 2, wherein the concentration of the alkaline substance in the mixed solution in the step (1) is 6-8 g/L; the concentration of the alkaline substance in the mixed solution in the step (2) is 12-14 g/L.
4. The preparation method of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst according to claim 1 or 2, wherein the cerium dioxide precursor in step (1) is Ce (NO)3)3·6H2O; the mass ratio of the cerium dioxide precursor to water is 1: (20-30);
the precursor of the ferrihydrite in the step (2) is Fe (NO)3)3·9H2O; the mass ratio of the hollow cerium dioxide nano microspheres to water is (0.2-1): 240.
5. the preparation method of the hollow cerium dioxide microsphere-supported ferrihydrite multiphase fenton-like catalyst according to claim 4, wherein the alkaline substance in the step (1) is NaOH, the alkaline substance is added in the form of an aqueous solution of the NaOH, and the mass concentration of the aqueous solution is 0.05-0.1 g/ml;
the alkaline substance in the step (2) is NaOH; the ferrihydrite precursor and the alkaline substance are added in the form of aqueous solution, wherein the mass ratio of the solute to the solvent in the ferrihydrite precursor aqueous solution is 0.227: (1-1.2), the mass concentration of the alkaline substance aqueous solution is 0.05-0.1 g/ml;
and simultaneously adding the ferrihydrite precursor aqueous solution and the alkaline substance aqueous solution in a dropwise manner, and completing dropwise addition within 5-10 min.
6. The preparation method of the hollow cerium dioxide microsphere-supported ferrihydrite multiphase fenton-like catalyst according to claim 3, wherein the standing and aging time in the step (1) is 12-14 h; and after the alkaline substance is added, oscillating treatment is carried out, wherein the oscillating speed is 160-180 rpm, and the oscillating time is 60-90 min.
7. The preparation method of the hollow cerium dioxide microsphere-supported ferrihydrite multiphase fenton-like catalyst according to claim 1 or 2, characterized in that the mixing in the step (1) is ultrasonic mixing, and the ultrasonic mixing time is 60-90 min; washing is carried out for 1-3 times by using ethanol and water respectively; the drying condition is vacuum drying for 6-16 h at 50-100 ℃;
the oscillation rate of the reaction in the step (2) is 160-180 rmp; centrifuging at 6000-8000 rpm for 10-15 min; the washing condition is that the product is respectively dispersed in ethanol and water and centrifuged, and the centrifugation is repeated for 1-3 times, wherein the centrifugation condition is that the product is centrifuged at 6000-8000 rpm for 10-15 min; the drying is freeze drying, and the drying is carried out for 24-36 hours at the temperature of-50 ℃.
8. The hollow cerium dioxide microspheres prepared by the method of any one of claims 1 to 7 are loaded with a ferrihydrite heterogeneous fenton-like catalyst.
9. The application of the hollow cerium dioxide microsphere-supported ferrihydrite heterogeneous fenton-like catalyst in the field of photo-fenton degradation of organic matters is characterized in that the application is removal of organic matters in wastewater.
10. The application of the hollow cerium dioxide microsphere loaded ferrihydrite multiphase fenton-like catalyst in the field of photo-fenton degradation of organic matters is characterized by comprising the following steps of: mixing hCeO2Mixing the/fh multiphase Fenton-like catalyst with the wastewater uniformly, oscillating and adsorbing the mixture under the condition of keeping out of the sun, adding H after the adsorption balance is achieved2O2Performing photo-Fenton catalytic degradation under a visible light source to finish degradation treatment on organic matters in the wastewater;
the hCeO2The adding amount of the/fh multiphase Fenton-like catalyst in the wastewater is 0.2-1.2 g/L; said H2O2The concentration of the wastewater is 20-100 mmol/L; the organic matter is at least one of antibiotic, tetrabromobisphenol A, rhodamine B and 2, 4-dichlorophenol; the antibiotic is tetracycline;
the concentration of the organic matters in the wastewater is 10-30 mg/L; the time of photo-Fenton catalytic degradation is 10-120 min; the method is carried out under the condition of illuminating low-energy-consumption LED lamps with the power of 5W.
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