CN113171777B - Iron/cerium bimetallic heterogeneous electro-Fenton catalyst and preparation method and application thereof - Google Patents
Iron/cerium bimetallic heterogeneous electro-Fenton catalyst and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 330
- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 129
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 79
- 230000003115 biocidal effect Effects 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 8
- 239000004098 Tetracycline Substances 0.000 claims description 63
- 229960002180 tetracycline Drugs 0.000 claims description 63
- 229930101283 tetracycline Natural products 0.000 claims description 63
- 235000019364 tetracycline Nutrition 0.000 claims description 63
- 150000003522 tetracyclines Chemical class 0.000 claims description 63
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 32
- 238000006555 catalytic reaction Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 235000013980 iron oxide Nutrition 0.000 claims description 24
- 238000005273 aeration Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011258 core-shell material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229960005091 chloramphenicol Drugs 0.000 claims description 2
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 229960000282 metronidazole Drugs 0.000 claims description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 34
- 229960005191 ferric oxide Drugs 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 238000005374 membrane filtration Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
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- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- -1 however Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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 an iron/cerium bimetallic heterogeneous electro-Fenton catalyst and a preparation method and application thereof. The preparation method comprises the following steps: dropwise adding sodium borohydride solution to the solution containing Fe3+And Ce3+Stirring the mixed solution, and aging the mixed solution to obtain the iron/cerium bimetallic heterogeneous electro-Fenton catalyst. The iron/cerium bimetallic heterogeneous electro-Fenton catalyst has the advantages of good catalytic activity, good stability, environmental friendliness and the like, is a novel heterogeneous electro-Fenton catalyst with excellent performance, can be used for treating antibiotic wastewater, can effectively remove antibiotics in the wastewater, and has high use value and good application prospect. The preparation method has the advantages of low requirement on equipment, simple operation, short time consumption, environmental protection and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of water treatment, relates to preparation and application of a heterogeneous electro-Fenton catalyst, and particularly relates to an iron/cerium bimetallic heterogeneous electro-Fenton catalyst and a preparation method and application thereof.
Background
Antibiotics have been widely used in the treatment of various human diseases and in animal husbandry. However, due to severe abuse, they have a large amount of residues in various water environments, thus causing adverse effects on human health and living environments indirectly or directly. Therefore, it is important to realize the high-efficiency treatment of antibiotic wastewater.
The Fenton process is one of Advanced Oxidation Processes (AOPs), and has attracted extensive attention in solving the pollution problem of toxic, difficult-to-degrade and non-biodegradable organic pollutants in global water due to its advantages of high efficiency, simplicity, low cost and the like. In order to overcome some of the inherent disadvantages and to improve the versatility and environmental friendliness thereof, the electro-fenton (EF) process is the most satisfactory technology. The electro-Fenton reaction is a promising advanced oxidation process that allows in situ generation of hydrogen peroxide (H)2O2) With Fe2+Fenton reaction takes place to generate hydroxyl radical (. OH, E) with strong oxidizing propertyθ2.8V). Hydroxyl radicals can react non-selectively with organic contaminants until they are completely mineralized to carbon dioxide, water and inorganic ions. Generation of H at the cathode2O2Potential risks of transportation, storage and handling thereof can be avoided. Compared with the traditional Fenton process, Fe3+Continuous electrochemical reduction to Fe at the cathode2+Provides a new way for further improving the degradation rate of pollutants. Therefore, the key point of effectively treating the organic pollutant wastewater by using the electro-Fenton technology is to obtain the electro-Fenton catalyst with strong catalytic capability.
At present, research shows that Fe/Ce bimetallic particles can be used as heterogeneous Fenton-like system catalysts, however, additives (such as an inducer and an oxidant) are still required to be additionally added in the use process of the existing heterogeneous electro-Fenton catalysts based on Fe/Ce bimetallic particles to effectively remove organic pollutants, the use of the additives inevitably increases the treatment cost, the treatment process is more complicated, the operation difficulty is increased, and the low-cost and high-efficiency removal of the organic pollutants in water is not facilitated. In addition, the existing preparation method of the heterogeneous electro-Fenton catalyst based on the Fe/Ce bimetallic particles still has the advantages of complex preparation process, long preparation time consumption, high requirement on equipment, high preparation cost and the like, and is not beneficial to realizing the wide application of the electro-Fenton technology in the treatment of organic pollutant wastewater. Therefore, a heterogeneous electro-Fenton catalyst with good catalytic activity, good stability and environmental friendliness, and a preparation method which is matched with the heterogeneous electro-Fenton catalyst and has the advantages of short time consumption, simplicity in operation, low equipment requirement, economy and environmental friendliness are urgently needed, and the method has a very important significance for effectively removing antibiotics in water by utilizing the electro-Fenton technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an iron/cerium bimetallic heterogeneous electro-Fenton catalyst with good catalytic activity, good stability and environmental friendliness, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
an iron/cerium bimetal heterogeneous electro-Fenton catalyst comprises nano zero-valent iron particles, wherein iron oxides are coated on the surfaces of the nano zero-valent iron particles to form a core-shell structure; the iron oxide is doped with cerium oxide.
In the iron/cerium bimetallic heterogeneous electro-Fenton catalyst, the mass ratio of the nano zero-valent iron particles to the iron oxide to the cerium oxide in the iron/cerium bimetallic heterogeneous electro-Fenton catalyst is 1: 2.86: 1.54.
In the above iron/cerium bimetallic heterogeneous electro-fenton catalyst, the further improvement is that the iron oxide comprises ferric oxide and ferrous oxide; the oxides of cerium include oxides of trivalent cerium and tetravalent cerium.
As a general technical concept, the present invention also provides a method for preparing the above iron/cerium bimetallic heterogeneous electro-fenton catalyst, comprising the steps of:
s1, dropwise adding the sodium borohydride solution to the solution containing Fe3+And Ce3+Stirring the mixed solution;
and S2, aging, washing and drying the stirred mixed solution in the step S1 to obtain the iron/cerium bimetal heterogeneous electro-Fenton catalyst.
In the above preparation method, further improvement, in step S1, the Fe-containing material3+And Ce3+Fe in the mixed solution of3+And Ce3+The molar ratio of (A) to (B) is 2: 1.
In step S1, the dropping rate of the sodium borohydride solution is 0.02 mL/S to 0.5 mL/S; the concentration of the sodium borohydride solution is 0.4M; the rotating speed of the stirring is 250 rpm; the stirring time is 10-15 min.
In the above preparation method, further improvement is provided, in step S2, the aging time is 2 hours; the washing is to wash the aged product by adopting ultrapure water or ethanol; the drying is carried out under vacuum conditions; the temperature of the drying was 60 ℃.
As a general technical concept, the invention also provides an application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treatment of antibiotic wastewater.
The application is further improved, and comprises the following steps: mixing an iron/cerium bimetallic heterogeneous electro-Fenton catalyst with the antibiotic wastewater to perform electro-Fenton catalytic reaction, thereby finishing the treatment of the antibiotic wastewater; the addition amount of the iron/cerium bimetal heterogeneous electro-Fenton catalyst is 0.04 to 0.12g of the iron/cerium bimetal heterogeneous electro-Fenton catalyst added in each liter of antibiotic wastewater.
In the above application, a further improvement is that the electro-fenton catalytic reaction process further comprises adding an electrolyte into the antibiotic wastewater; the addition amount of the electrolyte is 0.05mol of electrolyte added in each liter of antibiotic wastewater; the electrolyte is sodium sulfate.
In the above application, it is further improved that the electro-fenton catalytic reaction process further comprises performing aeration treatment on the antibiotic wastewater; the aeration treatment is to introduce oxygen-containing gas into the system; the aeration rate in the aeration treatment process is 0.1L/min.
In the above application, further improved, the antibiotic in the antibiotic wastewater is at least one of tetracycline, metronidazole and chloramphenicol; the initial concentration of the antibiotics in the antibiotic wastewater is 50 mg/L; the pH value of the antibiotic wastewater is 3-9; in the reaction system of the electro-Fenton catalytic reaction, activated carbon fibers are used as a cathode, and a Pt sheet is used as an anode; controlling the impressed current to be 15 mA-80 mA in the electro-Fenton catalytic reaction process; the electro-Fenton catalytic reaction is carried out under the condition of stirring; the rotating speed of the stirring is 500 rpm; the temperature of the electro-Fenton catalytic reaction is normal temperature; the time of the electro-Fenton catalytic reaction is 60 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides an iron/cerium bimetallic heterogeneous electro-Fenton catalyst, which takes nano zero-valent iron particles as an inner core, the surface of the nano zero-valent iron particles is coated with iron oxide to form a core-shell structure, and cerium oxide is doped in the iron oxide, so that the iron/cerium bimetallic heterogeneous electro-Fenton catalyst is a novel composite material of the nano zero-valent iron particles coated by the iron oxide and the cerium oxide. In the invention, the nanometer zero-valent iron particles and the iron oxide can induce the single electron molecular oxygen to activate to generate superoxide radical, and induce the double electron molecular oxygen to activate to generate H by respectively transferring electrons from the iron core to the ferrous ions and the surface of the iron oxide shell2O2Therefore, in the using process, no additive (such as oxidant hydrogen peroxide) is required to be added additionally, meanwhile, the surface of the cerium oxide contains a large number of oxygen vacancies due to the oxidation-reduction cycle of Ce (III)/Ce (IV), so that the generation of strong oxidative hydroxyl free radicals can be accelerated, trivalent cerium is similar to divalent iron and can activate hydrogen peroxide to generate hydroxyl free radicals, so that the iron oxide and the cerium oxide are coated on the surface of the nano zero-valent iron particles, and the cerium (Ce) can be remarkably improved3+/Ce4+) And iron (Fe)2+/Fe3+) The redox cycles of the composite material, thereby improving the catalytic activity of the composite material. Compared with other existing Fe/Ce bimetallic particle heterogeneous Fenton catalysts, the iron/cerium double gold provided by the inventionIn the heterogeneous electro-Fenton catalyst, nano zero-valent iron particles are used as an inner core, which can induce the activation of molecular oxygen to generate ferrous iron and hydrogen peroxide, and can further improve the catalytic activity on the premise of not additionally adding additives. The iron/cerium bimetallic heterogeneous electro-Fenton catalyst has the advantages of good catalytic activity, good stability, environmental friendliness and the like, is a novel heterogeneous electro-Fenton catalyst with excellent performance, can be used for treating antibiotic wastewater, can effectively remove antibiotics in the wastewater, and has high use value and good application prospect.
(2) In the iron/cerium bimetallic heterogeneous electro-Fenton catalyst, the mass ratio of the nano zero-valent iron particles to the iron oxide to the cerium oxide is optimized to be 1: 2.86: 1.54, so that the redox cycling action between iron and cerium is stronger, and the composite material can be ensured to have better catalytic activity, because when the content of cerium is too low, cerium (Ce) is not beneficial to formation3+/Ce4+) And iron (Fe)2+/Fe3+) When the content of cerium is too high, the content of iron is inevitably reduced, and when the content of iron is lower, the core-shell structure is not favorably formed, and in addition, the iron species are agglomerated due to the high content of iron, and the catalytic activity is also reduced; meanwhile, sufficient hydrogen peroxide can be generated in the using process of the catalyst, and the treatment cost can be obviously reduced on the basis of ensuring better catalytic activity.
(3) The preparation method of the iron/cerium bimetal heterogeneous electro-Fenton catalyst comprises the steps of3+And Ce3+The mixed solution is used as a raw material, sodium borohydride is used for reduction treatment, and then the iron/cerium bimetal heterogeneous electro-Fenton catalyst with a core-shell structure is formed through aging treatment. The preparation method has the advantages of low requirement on equipment, simple operation, short time consumption, environmental protection and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) The preparation method of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst provided by the invention comprises the following steps of optimizing the catalystFe3+And Ce3 +Fe in the mixed solution of3+And Ce3+The molar ratio of (1) to (2) is favorable for preparing the iron/cerium bimetallic heterogeneous electro-Fenton catalyst with better catalytic activity and stability, because when the molar ratio of iron to cerium is less than 2, the content of iron is low, which is not favorable for forming a core-shell structure, and when the molar ratio of iron to cerium is more than 2, the content of iron is high, which can cause iron species to agglomerate, thereby reducing the catalytic activity of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst.
(5) According to the preparation method of the iron/cerium bimetal heterogeneous electro-Fenton catalyst, the dropping speed of the sodium borohydride solution is optimized to be 0.02-0.5 mL/s, so that the prepared iron/cerium bimetal heterogeneous electro-Fenton catalyst is ensured to be in a core-shell structure, and the needed core-shell structure cannot be formed easily when the dropping speed is lower than 0.02 mL/s or higher than 0.5 mL/s; meanwhile, in the invention, the aging time is optimized to be 2h, which is beneficial to generating iron oxide and cerium oxide, and can enhance the coating effect of the iron oxide and the cerium oxide on the nano zero-valent iron, so that the iron oxide and the cerium oxide can be firmly coated on the surface of nano zero-valent iron particles, and the iron/cerium bimetal heterogeneous electro-Fenton catalyst with better stability is obtained, because the aging time is too low to generate the iron oxide and the cerium oxide, and the aging time is too high to cause the falling of the iron oxide and the cerium oxide coated outside the nano zero-valent iron core.
(6) The invention also provides an application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater, wherein the iron/cerium bimetal heterogeneous electro-Fenton catalyst and the antibiotic wastewater are mixed in an electro-Fenton system to perform catalytic oxidation reaction, and the catalytic oxidation reaction mainly comprises anodic oxidation, electro-Fenton reaction performed by ferrous iron and hydrogen peroxide, Fenton-like reaction performed by trivalent cerium and hydrogen peroxide and homogeneous Fenton reaction performed by dissolved small amount of metal ions, so that the effective removal of antibiotics in the wastewater can be realized by treating the iron/cerium bimetal heterogeneous electro-Fenton catalyst. The method for treating the antibiotic wastewater by using the iron/cerium bimetallic heterogeneous electro-Fenton catalyst has the advantages of low cost, mild reaction conditions, simple operation,Good removing effect, convenient separation and recovery, and the like, and simultaneously, the continuous in-situ generation of H in the reaction process is ensured by selecting the activated carbon fiber as the cathode2O2Without additional addition, thereby solving the problem of H2O2The method has the advantages of reducing the operation cost due to transportation, storage and other problems, being widely used for treating various antibiotic wastewater, and efficiently and thoroughly removing various antibiotics in the wastewater, which has very important significance for effectively treating the antibiotic wastewater.
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 is a TEM image of an Fe/Ce bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) in example 1 of the present invention.
FIG. 2 shows Fe/Ce bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and Fe-based heterogeneous electro-Fenton catalyst (Fe @ Fe) in example 1 of the present invention2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) XRD pattern of (a).
FIG. 3 shows examples 1 of the present invention including an iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) and an iron-based heterogeneous electro-Fenton catalyst (Fe @ Fe)2O3) The nitrogen adsorption-desorption graph of (a) is Fe: Ce 2: 1, and (b) is Fe @ Fe2O3。
FIG. 4 shows Fe/Ce bimetallic heterogeneous electro-Fenton catalysts (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and Fe-based heterogeneous electro-Fenton catalysts (Fe @ Fe) with different Fe and Ce molar ratios in example 2 of the present invention2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) The degradation effect of the tetracycline is shown.
FIG. 5 is an XPS chart of an iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) before and after use in example 2 of the present invention.
FIG. 6 is a graph showing the degradation effect of different amounts of Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water in example 3 of the present invention.
FIG. 7 is a graph showing the degradation effect of the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water of different pH values in example 4 of the present invention.
FIG. 8 is a graph showing the degradation effect of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water under different current conditions in example 5 of the present invention.
FIG. 9 is a graph showing the effect of the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on the degradation of tetracycline waste water under different aeration conditions in example 6 of the present invention.
FIG. 10 is a graph showing the effect of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst on the cyclic degradation of tetracycline waste water in example 7 of the present invention.
FIG. 11 is a graph showing the elution effect of Fe and Ce when the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst is used for cyclic treatment of tetracycline waste water 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 following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1
An iron/cerium bimetal heterogeneous electro-Fenton catalyst is characterized in that an inner shell is formed by nanometer zero-valent iron particles, iron oxide is coated on the surfaces of the nanometer zero-valent iron particles to form a core-shell structure, and cerium oxide is doped in the iron oxide.
In this example, the mass ratio of the nano zero-valent iron particles, the iron oxide, and the cerium oxide in the iron/cerium bimetallic heterogeneous electro-fenton catalyst is 1: 2.86: 1.54.
In this embodiment, the iron oxide includes ferric oxide and ferrous oxide; the oxides of cerium include oxides of trivalent cerium and oxides of tetravalent cerium.
A method for preparing the iron/cerium bimetallic heterogeneous electro-fenton catalyst in the embodiment includes the following steps:
(1) dissolving ferric chloride and cerous nitrate into 200mL of ultrapure water in sequence according to the molar ratio of 2: 1 at room temperature to obtain the product containing Fe3+And Ce3+The mixed solution of (1).
(2) 0.4M NaBH was added at a drop rate of 0.5 mL/sec4Gradually dropwise adding the solution containing Fe obtained in the step (1)3+And Ce3+In the mixed solution, a reaction system is stirred by a stirring device at the rotating speed of 250rpm in the dropping process, and the stirring is continued for 10min after the dropping is finished.
(3) Aging the particles generated after the reaction in the step (2) in a solution for 2h, then centrifugally washing the particles for three times by using ultrapure water or ethanol, and drying the particles at 60 ℃ under a vacuum condition to obtain the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst (Fe @ Fe)2O3-CeO2) And is recorded as Fe: Ce of 2: 1.
In example 1, iron/cerium bimetallic heterogeneous electro-Fenton catalysts with different iron and cerium molar ratios were also prepared, containing Fe3+And Ce3+When the molar ratio of Fe to Ce in the mixed solution is 4: 1 and 1: 1, the corresponding Fe/Ce bimetal heterogeneous electro-Fenton catalyst is recorded as Fe: Ce 4: 1 and Fe: Ce 1: 1 in sequence.
In example 1, an iron-based heterogeneous electro-Fenton catalyst (Fe @ Fe) was also prepared2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) The preparation method is the same as that of example 1.
FIG. 1 is a TEM image of an Fe/Ce bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) in example 1 of the present invention. As can be seen from FIG. 1, the iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe @ Fe) of the present invention2O3-CeO2) A typical core-shell structure is shown, with a diameter of about 100 nm.
FIG. 2 shows Fe/Ce bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and Fe-based heterogeneous electro-Fenton catalyst (Fe @ Fe) in example 1 of the present invention2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) XRD pattern of (a). As can be seen from FIG. 2, CeO2Doped with p-Fe @ Fe2O3The structure of (a) has no significant effect.
FIG. 3 shows examples 1 of the present invention including an iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) and an iron-based heterogeneous electro-Fenton catalyst (Fe @ Fe)2O3) The nitrogen adsorption-desorption graph of (a) is Fe: Ce 2: 1, and (b) is Fe @ Fe2O3. As shown in fig. 3, the specific surface area and pore size of the catalyst were characterized by a specific surface area and pore size analyzer (ASAP 2020), and the results were: the iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce 2: 1) has a specific surface area of 187.7m2Per g, pore volume of 0.37cm3Per g, and iron-based heterogeneous electro-Fenton catalyst (Fe @ Fe)2O3) Has a specific surface area of 38.4m2Per g, pore volume of 0.076cm3/g。
Example 2
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater specifically comprises the following steps of:
the iron/cerium bimetallic heterogeneous electro-fenton catalysts prepared in example 1 in different iron to cerium molar ratios (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and the iron-based heterogeneous electro-fenton catalyst (Fe @ Fe ═ 1) were weighed in an amount of 0.08g/L2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) Adding into tetracycline wastewater with initial concentration of 50mg/L, pH value of 3.85, respectively, placing on a constant temperature stirrer, stirring for 30min to reach adsorption saturation of tetracycline, adding anhydrous sodium sulfate, stirring to dissolve completely to make the concentration of system sodium sulfate be 0.05M, inserting into anode and cathode, wherein the cathode is Active Carbon Fiber (ACF), the anode is platinum (Pt) sheet, introducing air into the system, controlling aeration rate to be 0.1L/min to provide enough dissolved oxygen to generate hydrogen peroxide at the cathode, applying 50mA constant current power supply, and performing electro-Fenton catalytic reaction at room temperature (25 deg.C) and stirring speed of 500rpm for 60MAnd in, finishing the treatment of the tetracycline wastewater.
Anodic oxidation: the blank was prepared by the same conditions without any catalyst.
In the electro-Fenton catalytic reaction process, 0.5mL of sample is taken out of the solution at regular intervals, 3.5mL of deionized water is added for mixing, the membrane filtration is carried out by using a 0.22 μm membrane, and the taken sample is tested by using an ultraviolet-visible spectrophotometer to determine the tetracycline removal rate of the catalyst, and the result is shown in FIG. 4.
FIG. 4 shows Fe/Ce bimetallic heterogeneous electro-Fenton catalysts (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and Fe-based heterogeneous electro-Fenton catalysts (Fe @ Fe) with different Fe and Ce molar ratios in example 2 of the present invention2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) The degradation effect of the tetracycline is shown. As can be seen from FIG. 4, the Fe/Ce bimetallic heterogeneous electro-Fenton catalysts (Fe: Ce 4: 1, Fe: Ce 2: 1, Fe: Ce 1: 1) and the Fe-based heterogeneous electro-Fenton catalysts (Fe @ Fe) with different Fe and Ce molar ratios2O3) And cerium-based heterogeneous electro-Fenton catalyst (CeO)2) After the electro-Fenton catalytic treatment is carried out for 60min, the removal rates of the tetracycline are 79.8%, 90.7%, 78.5%, 71.2% and 55.6% in sequence. It can be seen that the degradation efficiency of TC can be further improved by using the iron/cerium bimetallic heterogeneous electro-fenton catalyst of the present invention, and the iron/cerium bimetallic heterogeneous electro-fenton catalyst with Fe: Ce of 2: 1 has the highest catalytic activity for TC, probably due to Ce4+/Ce3+And Fe3+/Fe2+The catalyst has optimal synergistic effect in the catalytic process; in addition, the iron/cerium bimetal heterogeneous electro-Fenton catalyst (Fe: Ce: 2: 1) can adsorb and remove 17.6 percent of tetracycline in 30 min; the anode oxidation effect leads the removal rate to reach 34.1 percent under the condition of not adding a catalyst. In addition, the elution amount of iron ions and cerium ions in the reaction solution is 1.0mg/L and 0.78mg/L respectively, which shows that the catalyst has better stability and cannot cause secondary pollution to the environment.
FIG. 5 is an XPS chart of an iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce ═ 2: 1) before and after use in example 2 of the present invention. As can be seen from fig. 5, before use, Fe, Ce and O elements are present in a sample of the iron/cerium bimetallic heterogeneous electro-fenton catalyst (Fe: Ce ═ 2: 1), and after use, XPS spectra of O1s, Fe2p and Ce3d show similar characteristics as before reaction, confirming that the catalyst has good cyclability and stability.
Example 3
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater specifically comprises the following steps of:
weighing the iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce is 2: 1) prepared in example 1 according to the adding amount of 0.04g/L, 0.06g/L, 0.08g/L and 0.12g/L, respectively adding the iron/cerium bimetallic heterogeneous electro-Fenton catalyst into tetracycline wastewater with the initial concentration of 50mg/L, pH value of 3.85, placing the tetracycline wastewater on a constant-temperature stirrer, stirring for 30min to reach the adsorption saturation of tetracycline, adding anhydrous sodium sulfate, stirring until the anhydrous sodium sulfate is completely dissolved, enabling the concentration of the system sodium sulfate to be 0.05M, inserting an anode and a cathode, wherein the cathode is Activated Carbon Fiber (ACF), the anode is a platinum (Pt) sheet, introducing air into the system, controlling the aeration rate to be 0.1L/min to provide enough dissolved oxygen to generate hydrogen peroxide at the cathode, applying a constant current power supply of 50mA, and carrying out electro-Fenton catalytic reaction for 60min at the normal temperature (25 ℃) and the stirring speed of 500rpm, and finishing the treatment of the tetracycline wastewater.
In the electro-Fenton catalytic reaction process, 0.5mL of sample is taken out of the solution at regular intervals, 3.5mL of deionized water is added for mixing, the membrane filtration is carried out by using a 0.22 μm membrane, and the taken sample is tested by using an ultraviolet-visible spectrophotometer to determine the tetracycline removal rate of the catalyst, and the result is shown in FIG. 6.
FIG. 6 is a graph showing the degradation effect of different amounts of Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water in example 3 of the present invention. As can be seen from FIG. 6, in the present invention, when the amounts of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst added were 0.04g/L, 0.06g/L, 0.08g/L, and 0.12g/L, the tetracycline removal rates after 60min of electro-Fenton catalytic treatment were 65.9%, 74.9%, 90.7%, and 86.3%, respectively. With the increase of the catalyst addition, the active sites correspondingly increase, thereby promoting the generation of hydroxyl radicals in the heterogeneous electro-Fenton reaction. When the amount of the addition is increased to 0.12g/L, the tetracycline removal rate is correspondingly decreased due to the occurrence of side reactions. Therefore, the amount of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst added was 0.08g/L as the best choice for the subsequent examples.
Example 4
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater specifically comprises the following steps of:
weighing 5 parts of the iron/cerium bimetallic heterogeneous electro-fenton catalyst (Fe: Ce is 2: 1) prepared in example 1 according to the addition amount of 0.08g/L, respectively adding the iron/cerium bimetallic heterogeneous electro-fenton catalyst into tetracycline wastewater (the initial concentration is 50mg/L) with the pH values of 3, 3.85, 5, 7 and 9, placing the tetracycline wastewater on a constant-temperature stirrer, stirring for 30min to reach the adsorption saturation of tetracycline, adding anhydrous sodium sulfate, stirring until the sodium sulfate is completely dissolved to ensure that the concentration of the system sodium sulfate is 0.05M, inserting an anode and a cathode, wherein the cathode is Activated Carbon Fiber (ACF), the anode is a platinum (Pt) sheet, introducing air into the system, controlling the aeration rate to be 0.1L/min to provide enough dissolved oxygen to generate hydrogen peroxide at the cathode, applying a constant current power supply of 50mA, carrying out electro-fenton catalytic reaction for 60min at the normal temperature (25 ℃) and the stirring speed of 500rpm, and finishing the treatment of the tetracycline wastewater.
In the electro-Fenton catalytic reaction process, 0.5mL of sample is taken out of the solution at regular intervals, 3.5mL of deionized water is added for mixing, the membrane filtration is carried out by using a 0.22 μm membrane, and the taken sample is tested by using an ultraviolet-visible spectrophotometer to determine the tetracycline removal rate of the catalyst, and the result is shown in FIG. 7.
FIG. 7 is a graph showing the degradation effect of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water having different pH values in example 4 of the present invention. As can be seen from FIG. 7, the removal rates of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst for tetracycline wastewater with pH values of 3, 3.85, 5, 7 and 9 are 92.6%, 90.7%, 82.7%, 80.7% and 67.8% in sequence. It can be seen that the stronger the acidity, the more favorable the generation of hydrogen peroxide and hydroxyl radicals in the fenton reaction, thereby promoting the degradation of tetracycline. At a pH of 3.85, the iron/cerium bimetallic heterogeneous electro-Fenton catalyst has a tetracycline removal rate as high as 90.7%. In addition, the pH value of the antibiotic wastewater is between 3 and 4 in general, which can avoid additionally adopting a pH regulator to adjust the pH value of the system, thereby being capable of reducing the treatment, and the catalyst of the invention is an economical catalyst capable of reducing the treatment cost.
Example 5
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treatment of antibiotic wastewater specifically is to treat tetracycline wastewater by using the iron/cerium bimetal heterogeneous electro-Fenton catalyst, and comprises the following steps:
weighing 4 parts of the iron/cerium bimetallic heterogeneous electro-fenton catalyst (Fe: Ce is 2: 1) prepared in example 1 according to the addition amount of 0.08g/L, respectively adding the iron/cerium bimetallic heterogeneous electro-fenton catalyst into tetracycline wastewater with the initial concentration of 50mg/L, pH value of 3.85, placing the tetracycline wastewater on a constant-temperature stirrer, stirring the tetracycline wastewater for 30min to reach adsorption saturation, adding anhydrous sodium sulfate, stirring the tetracycline until the sodium sulfate is completely dissolved so that the concentration of the system sodium sulfate is 0.05M, inserting an anode and a cathode, wherein the cathode is an Activated Carbon Fiber (ACF), the anode is a platinum (Pt) sheet, introducing air into the system, controlling the aeration rate to be 0.1L/min to provide enough dissolved oxygen to generate hydrogen peroxide at the cathode, respectively applying constant current power supplies of 15mA, 30mA, 50mA and 80mA, and carrying out electro-fenton catalytic reaction for 60min at the normal temperature (25 ℃) and the stirring speed of 500rpm, and finishing the treatment of the tetracycline wastewater.
In the electro-Fenton catalytic reaction process, 0.5mL of sample is taken out of the solution at regular intervals, 3.5mL of deionized water is added for mixing, the membrane filtration is carried out by using a 0.22 μm membrane, and the taken sample is tested by using an ultraviolet-visible spectrophotometer to determine the tetracycline removal rate of the catalyst, and the result is shown in FIG. 8.
FIG. 8 is a graph showing the degradation effect of the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on tetracycline waste water under different current conditions in example 5 of the present invention. As can be seen from FIG. 8, the removal rates of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst for tetracycline wastewater in electro-Fenton systems with applied currents of 15mA, 30mA, 50mA and 80mA were 59.5%, 72.9%, 90.7% and 82.2% in sequence, and it can be seen that the generation amount of hydrogen peroxide increased with the increase of applied current, which is beneficial to the degradation of tetracycline. When the applied current is increased to 80mA, since the activation capacity of the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst for hydrogen peroxide is limited at a fixed catalyst dosage, the excessive hydrogen peroxide reacts with hydroxyl radicals to generate superoxide hydrogen radicals with oxidation capacity far lower than that of the hydroxyl radicals. Therefore, applying a constant current of 50mA is the best choice for the subsequent embodiments.
Example 6
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater specifically comprises the following steps of:
weighing 2 parts of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst (Fe: Ce is 2: 1) prepared in example 1 according to the addition amount of 0.08g/L, respectively adding the iron/cerium bimetallic heterogeneous electro-Fenton catalyst into tetracycline wastewater with the initial concentration of 50mg/L, pH value of 3.85, placing the tetracycline wastewater on a constant-temperature stirrer, stirring the tetracycline wastewater for 30min to reach adsorption saturation, adding anhydrous sodium sulfate, stirring the tetracycline until the tetracycline is completely dissolved so that the concentration of the system sodium sulfate is 0.05M, inserting an anode and a cathode, wherein the cathode is an Activated Carbon Fiber (ACF), the anode is a platinum (Pt) sheet, respectively carrying out treatment under natural aeration (without air, the aeration rate is controlled to be 0.1L/min) and manual aeration (with air, the aeration rate is controlled to be 0.1L/min), simultaneously applying a constant current power supply of 50mA, carrying out electro-Fenton catalytic reaction for 60min at the normal temperature (25 ℃) and the stirring speed of 500rpm, and finishing the treatment of the tetracycline wastewater.
In the electro-Fenton catalytic reaction process, 0.5mL of sample is taken out of the solution at regular intervals, 3.5mL of deionized water is added for mixing, the membrane filtration is carried out by using a 0.22 μm membrane, and the taken sample is tested by using an ultraviolet-visible spectrophotometer to determine the tetracycline removal rate of the catalyst, and the result is shown in FIG. 9.
FIG. 9 is a graph showing the effect of the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst on the degradation of tetracycline waste water under different aeration conditions in example 6 of the present invention. As can be seen from FIG. 9, the removal rates of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst for tetracycline wastewater in an electro-Fenton system with 0.1L/min of natural aeration and artificial aeration are 58.7% and 90.7% in sequence. In order to provide efficient and satisfactory tetracycline removal performance, an appropriate aeration amount is essential, so we chose artificial aeration of 0.1L/min as the best choice for the subsequent examples.
Example 7
The application of the iron/cerium bimetal heterogeneous electro-Fenton catalyst in treating antibiotic wastewater specifically relates to a method for circularly treating tetracycline wastewater by using the iron/cerium bimetal heterogeneous electro-Fenton catalyst, which comprises the following steps:
(1) the iron/cerium bimetallic heterogeneous electro-Fenton catalyst prepared in example 1 (Fe: Ce 2: 1) was weighed in an amount of 0.08g/L and added to tetracycline waste water having an initial concentration of 50mg/L, pH value of 3.85, placing on a constant temperature stirrer, stirring for 30min to reach tetracycline adsorption saturation, adding anhydrous sodium sulfate, stirring to dissolve completely to make the concentration of sodium sulfate be 0.05M, inserting anode and cathode, wherein the cathode is Active Carbon Fiber (ACF), the anode is platinum (Pt) sheet, air is introduced into the system, the aeration rate is controlled to be 0.1L/min, to provide enough dissolved oxygen to generate hydrogen peroxide at the cathode, a constant current source of 50mA was applied, the electro-Fenton catalytic reaction is carried out for 60min at the normal temperature (25 ℃) and the stirring speed of 500rpm, and the treatment of the tetracycline wastewater is finished.
(2) Separating the catalyst from the reaction system in the step (1), and after treatment, continuously treating the tetracycline waste water for 5 times according to the method in the step (1).
After each electro-Fenton reaction, 0.5mL of sample was removed from the solution, 3.5mL of deionized water was added and mixed, filtered through a 0.22 μm membrane, and the removed sample was tested with an ultraviolet-visible spectrophotometer to determine the removal rate of tetracycline by the catalyst, as shown in FIGS. 10 and 11.
FIG. 10 is a graph showing the effect of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst on the cyclic degradation of tetracycline waste water in example 7 of the present invention. As can be seen from FIG. 10, the removal rate and mineralization rate of tetracycline wastewater in 1, 2, 3, 4, and 5 cycles of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst of the present invention are 90.7%/86.9%, 88.6%/83.8%, 86.4%/81.9%, 82.9%/80.1%, and 80.1%/78%, respectively. With the increase of the recycling times, the removal rate and the mineralization rate of the tetracycline waste water are reduced in sequence because iron and cerium in the catalyst are correspondingly lost in each recovery treatment.
FIG. 11 is a graph showing the elution effect of Fe and Ce in the treatment of tetracycline waste water by the Fe/Ce bimetallic heterogeneous electro-Fenton catalyst in the example 7 of the present invention. As can be seen from FIG. 11, the iron and cerium elutions in the case of 1, 2, 3, 4, and 5 cycles of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst of the present invention were 1.0mg/L/0.78mg/L, 0.86mg/L/0.65mg/L, 0.73mg/L/0.51mg/L, 0.61mg/L/0.42mg/L, and 0.49mg/L/0.33mg/L, respectively. With the increase of the recycling times, the elution amount of iron/cerium is reduced in turn because iron and cerium in the catalyst are correspondingly lost in each recycling treatment, which shows that the iron/cerium bimetallic heterogeneous electro-Fenton catalyst has good stability.
From the above results, it can be seen that in the iron/cerium bimetallic heterogeneous electro-fenton catalyst, the nano zero-valent iron particles are used as the core, which can induce the molecular oxygen to activate to generate ferrous iron and hydrogen peroxide, and can further improve the catalytic activity without adding an additive, and meanwhile, the core-shell structure of the catalyst is more suitable for practical application, can prevent the material from spontaneous combustion in the air, and is beneficial to transportation and storage.
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 (8)
1. The iron/cerium bimetal heterogeneous electro-Fenton catalyst is characterized by comprising nano zero-valent iron particles, wherein iron oxides are coated on the surfaces of the nano zero-valent iron particles to form a core-shell structure; cerium oxide is doped in the iron oxide; the mass ratio of the nano zero-valent iron particles, the iron oxide and the cerium oxide in the iron/cerium bimetal heterogeneous electro-Fenton catalyst is 1: 2.86: 1.54; the iron/cerium bimetallic heterogeneous electro-Fenton catalyst is prepared by the following method:
(1) dropwise adding sodium borohydride solution to the solution containing Fe3+And Ce3+Stirring the mixed solution; the dropping speed of the sodium borohydride solution is 0.02 mL/s-0.5 mL/s; the concentration of the sodium borohydride solution is 0.4M; the rotating speed of the stirring is 250 rpm; the stirring time is 10-15 min;
(2) aging, washing and drying the mixed solution stirred in the step (1) to obtain an iron/cerium bimetal heterogeneous electro-Fenton catalyst; the aging time is 2 h; the washing is to wash the aged product by adopting ultrapure water or ethanol; the drying is carried out under vacuum conditions; the temperature of the drying was 60 ℃.
2. The iron/cerium bimetallic heterogeneous electro-fenton catalyst according to claim 1, wherein the iron oxide comprises ferric oxide and ferrous oxide; the oxides of cerium include oxides of trivalent cerium and tetravalent cerium.
3. A method for preparing an iron/cerium bimetallic heterogeneous electro-fenton catalyst according to claim 1 or 2, comprising the steps of:
S1、dropwise adding sodium borohydride solution to the solution containing Fe3+And Ce3+Stirring the mixed solution; said Fe-containing3+And Ce3+Fe in the mixed solution of3+And Ce3+The molar ratio of (A) to (B) is 2: 1; the dropping rate of the sodium borohydride solution is 0.02 mL/s-0.5 mL/s;
s2, aging, washing and drying the mixed solution stirred in the step S1 to obtain the iron/cerium bimetallic heterogeneous electro-Fenton catalyst; the aging time is 2 h.
4. The production method according to claim 3, wherein in step S1, the concentration of the sodium borohydride solution is 0.4M; the rotating speed of the stirring is 250 rpm; the stirring time is 10-15 min.
5. The production method according to claim 3 or 4, wherein in step S2, the washing is carried out by washing the product obtained after aging with ultrapure water or ethanol; the drying is carried out under vacuum conditions; the temperature of the drying was 60 ℃.
6. The use of the iron/cerium bimetallic heterogeneous electro-Fenton catalyst according to claim 1 or 2 or the iron/cerium bimetallic heterogeneous electro-Fenton catalyst prepared by the preparation method according to any one of claims 3 to 5 in the treatment of antibiotic wastewater.
7. Use according to claim 6, characterized in that it comprises the following steps: mixing an iron/cerium bimetal heterogeneous electro-Fenton catalyst with the antibiotic wastewater to perform electro-Fenton catalytic reaction to complete the treatment of the antibiotic wastewater; the addition amount of the iron/cerium bimetal heterogeneous electro-Fenton catalyst is 0.04g to 0.12g of the iron/cerium bimetal heterogeneous electro-Fenton catalyst added in each liter of antibiotic wastewater.
8. The use of claim 7, wherein the electro-Fenton catalytic reaction process further comprises adding an electrolyte to the antibiotic wastewater; the addition amount of the electrolyte is 0.05mol of electrolyte added in each liter of antibiotic wastewater; the electrolyte is sodium sulfate; the electro-Fenton catalytic reaction process also comprises the step of carrying out aeration treatment on the antibiotic wastewater; the aeration treatment is to introduce oxygen-containing gas into the system; the aeration rate in the aeration treatment process is 0.1L/min; the antibiotic in the antibiotic wastewater is at least one of tetracycline, metronidazole and chloramphenicol; the initial concentration of the antibiotics in the antibiotic wastewater is 50 mg/L; the pH value of the antibiotic wastewater is 3-9; in the reaction system of the electro-Fenton catalytic reaction, activated carbon fibers are used as a cathode, and a Pt sheet is used as an anode; controlling the impressed current to be 15 mA-80 mA in the electro-Fenton catalytic reaction process; the electro-Fenton catalytic reaction is carried out under the condition of stirring; the rotating speed of the stirring is 500 rpm; the temperature of the electro-Fenton catalytic reaction is normal temperature; the time of the electro-Fenton catalytic reaction is 60 min.
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| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| CN105562013A (en) * | 2016-01-08 | 2016-05-11 | 清华大学 | Nano Ce<0> doped Fe<0> composite material, preparation method and application method thereof |
| CN110694632A (en) * | 2019-10-22 | 2020-01-17 | 湘潭大学 | Preparation method and application of cobalt-cerium composite oxide catalyst |
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| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| CN105562013A (en) * | 2016-01-08 | 2016-05-11 | 清华大学 | Nano Ce<0> doped Fe<0> composite material, preparation method and application method thereof |
| CN110694632A (en) * | 2019-10-22 | 2020-01-17 | 湘潭大学 | Preparation method and application of cobalt-cerium composite oxide catalyst |
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