CN113862307B - Transition metal doped iron-manganese composite oxide and preparation method and application thereof - Google Patents
Transition metal doped iron-manganese composite oxide and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 46
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000001963 growth medium Substances 0.000 claims description 24
- 238000012258 culturing Methods 0.000 claims description 19
- 238000000197 pyrolysis Methods 0.000 claims description 17
- FABPRXSRWADJSP-MEDUHNTESA-N moxifloxacin Chemical compound COC1=C(N2C[C@H]3NCCC[C@H]3C2)C(F)=CC(C(C(C(O)=O)=C2)=O)=C1N2C1CC1 FABPRXSRWADJSP-MEDUHNTESA-N 0.000 claims description 16
- 229960003702 moxifloxacin Drugs 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 13
- 241000589776 Pseudomonas putida Species 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000001888 Peptone Substances 0.000 claims description 3
- 108010080698 Peptones Proteins 0.000 claims description 3
- 229940041514 candida albicans extract Drugs 0.000 claims description 3
- 235000019319 peptone Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012138 yeast extract Substances 0.000 claims description 3
- 239000013028 medium composition Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 6
- 230000004060 metabolic process Effects 0.000 abstract description 4
- 241000021561 Pseudomonas sp. F2 Species 0.000 abstract description 3
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- UOJLTGJDEASXFF-UHFFFAOYSA-N [Mn].[Co].[Fe] Chemical compound [Mn].[Co].[Fe] UOJLTGJDEASXFF-UHFFFAOYSA-N 0.000 description 20
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/36—Organic compounds containing halogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a transition metal doped ferro-manganese composite oxide and a preparation method thereof, wherein the transition metal ions are oxidized into high-valence oxides by using the biological activity and the growth metabolism process of Pseudomonas sp.F2, and meanwhile, the biological ferro-manganese oxides are used as carriers to oxidize and adsorb the metal ions on the surface of the biological ferro-manganese oxides, and the generated precipitate is the biological ferro-manganese composite oxide excessively doped with the metal ions. The metabolic process of the biological iron-manganese oxide and the newly-grown active cells converts transition metal ions into transition metal doped iron-manganese composite oxides with rich valence states and large specific surface areas.
Description
Technical Field
The invention belongs to the technical field of biomass materials, and particularly relates to a transition metal doped iron-manganese composite oxide, a preparation method and application thereof.
Background
Antibiotics are widely used for the treatment of human and animal diseases due to their broad-spectrum antibacterial properties. The antibiotics are metabolized very low in human body, 80% of the antibiotics are discharged out of the body along with urine and feces, and finally discharged into water body to pollute water environment. The concentration of antibiotics in surface water is in the range of ng/L-mug/L, but the concentration in hospital wastewater can reach several mg/L, which has potential danger to environment and human beings.
The persulfate advanced oxidation process is based on sulfate radicals (SO 4 - Of the persulphates, the persulphates being activated to give reactive groups (. OH, SO) 4 - 、· 1 O 2 And degrading organic matters with high efficiency. Transition metal (Co) 2+ 、Cu 2+ 、Ni 2 + And Ce (Ce) 2+ Etc.) can activate persulfates, but homogeneous reactions cause secondary pollution, and thus the preparation of solid catalysts has attracted attention from the scholars. Most catalysts are synthesized by chemical methods, the preparation conditions are severe and the cost is high, and biocatalysts are attracting attention of many scholars due to the mild preparation conditions, low cost and environmental friendliness.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a transition metal doped iron-manganese composite oxide, a preparation method and application thereof.
The invention provides a biological preparation method of transition metal doped ferro-manganese composite oxide, which comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Placing the culture medium in a constant temperature gas bath table, setting the culture temperature at 165rpm, continuously adding a transition metal solution into the culture medium after culturing for 1-3 days, and continuously culturing for 4-10 days;
(2) Standing and precipitating the culture medium after the culture in the step (1) to obtain black precipitate, pouring out supernatant, performing pyrolysis on the black precipitate and residual biological cells together, setting pyrolysis temperature and pyrolysis time, and performing pyrolysis to obtain the transition metal doped iron-manganese composite oxide.
Preferably, the culture temperature in step (1) is 20-40 ℃.
Preferably, the medium in step (1) contains Fe 2+ The concentration is 100-1000 mg/L, mn 2+ The concentration is 20-100 mg/L, fe in the culture medium 2+ ：Mn 2+ The concentration ratio is 5-10: 1.
preferably, the medium composition in step (1) comprises: peptone with final concentration of 1290mg/L, yeast extract powder with final concentration of 320mg/L, K with final concentration of 240mg/L 2 HPO 4 ·3H 2 MgSO of O, 320mg/L 4 ·7H 2 O, 240mg/L CaCl 2 ·2H 2 O, 120mg/L NaNO 3 NH of 150mg/L 4 Cl。
Preferably, the transition metal solution in step (1) contains Co 2+ 、Cu 2+ 、Ni 2+ And Ce (Ce) 2+ Any one or more metal ions.
Preferably, the concentration of metal ions in the transition metal solution in the step (1) is 0.02 to 1.0g/L.
Preferably, the pyrolysis temperature in the step (2) is 200 ℃, 400 ℃ or 600 ℃ and the pyrolysis time is 2h.
The invention also provides the transition metal doped iron-manganese composite oxide prepared by the biological preparation method of the transition metal doped iron-manganese composite oxide.
The invention also provides an application of the transition metal doped iron-manganese composite oxide in treating organic pollutants in sewage.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes pseudomonas putida to contain Fe 2+ And Mn of 2+ The culture medium of the preparation method is used for preparing the ferro-manganese oxide, and the transition metal doped ferro-manganese composite oxide is prepared by doping transition metal ions.
2. Compared with the chemical iron-manganese-cobalt composite oxide, the degradation rate of the biological iron-manganese-cobalt composite oxide prepared by the invention is faster than the rate of activating Peroxymonosulfate (PMS) to degrade Moxifloxacin (MOX), which is 6 times that of the chemical iron-manganese-cobalt composite oxide; compared with biological manganese oxide, the biological iron-manganese-cobalt composite oxide can more effectively activate peroxymonosulfate to degrade pollutants, the reaction rate of the biological iron-manganese-cobalt composite oxide is 28 times of that of undoped transition metal cobalt when the concentration of doped cobalt is 120mg/L, and the biological iron-manganese-cobalt composite oxide has the characteristics of economy and high efficiency from the preparation mode to the degradation efficiency.
3. The metabolic process of the biological iron-manganese oxide and the newly-grown active cells converts transition metal ions into transition metal doped iron-manganese composite oxides with rich valence states and large specific surface areas.
The foregoing is merely an overview of the technical solutions of the present invention, and for the sake of better understanding of the technical means of the present invention, the present invention is further described below mainly by taking biological iron-manganese-cobalt composite oxide activated PMS degradation MOX as an example, with reference to the accompanying drawings.
Drawings
FIG. 1 is a graph showing the effect of different transition metal doped iron-manganese composite oxides prepared by the invention on activating PMS and degrading MOX;
FIG. 2 is an X-ray photoelectron spectrum of the biological iron-manganese-cobalt composite oxide prepared by the invention;
FIG. 3 is a graph showing the removal effect of the chemical iron-manganese-cobalt composite oxide and the biological iron-manganese-cobalt composite oxide on the activation of the peroxymonosulfate to degrade moxifloxacin;
fig. 4 is a graph showing the removal effect of the addition amount of cobalt with different concentrations on the degradation of moxifloxacin by activating the peroxymonosulfate with the biological iron-manganese-cobalt composite oxide.
Detailed Description
The invention will be further described with reference to examples for the understanding of the invention. Wherein the culture medium comprises the following components: peptone with final concentration of 1290mg/L, yeast extract powder with final concentration of 320mg/L, K with final concentration of 240mg/L 2 HPO 4 ·3H 2 MgSO of O, 320mg/L 4 ·7H 2 O, 240mg/L CaCl 2 ·2H 2 O, 120mg/L NaNO 3 NH of 150mg/L 4 Cl。
Example 1
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in a constant temperature gas bath shaker at 165rpm and 30 deg.C for 2 days, and continuously adding 120mg/L transition metal Ni to the culture medium 2+ The solution is cultured for 5 days;
(2) Standing and precipitating the culture medium after culturing in the step (1) to obtain black precipitate, pouring out supernatant, pyrolyzing the black precipitate and residual biological cells together at 400 ℃ for 2 hours, and obtaining the transition metal doped ferromanganese composite oxide labeled as Bio-FeMnNiO after pyrolysis x 。
Example 2
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in a constant temperature gas bath shaker at 165rpm and 30 deg.C for 2 days, and continuously adding 120mg/L transition metal Co to the culture medium 2+ The solution is cultured for 5 days;
(2) Standing and precipitating the culture medium after culturing in the step (1) to obtain black precipitate, pouring out supernatant, pyrolyzing the black precipitate and residual biological cells together at 400 ℃ for 2 hours, and obtaining the transition metal doped ferromanganese composite oxide labeled as Bio-FeMnCoO after pyrolysis x 。
Example 3
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in a constant temperature gas bath shaker at 165rpm and 30 deg.C for 2 days, and continuously adding 120mg/L transition metal Cu to the culture medium 2+ The solution is cultured for 5 days;
(2) Standing and precipitating the culture medium after culturing in the step (1) to obtain black precipitate, pouring out supernatant, pyrolyzing the black precipitate and residual biological cells together at 400 ℃ for 2 hours, and obtaining the transition metal doped ferromanganese composite oxide labeled as Bio-FeMnCuO after pyrolysis x 。
Example 4
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in a medium of (2) a constant temperature gas bath shaker at 165rpm and 30 deg.C for 2 days, and continuously adding 120mg/L transition metal Ce to the medium 2+ The solution is cultured for 5 days;
(2) Standing and precipitating the culture medium after culturing in the step (1) to obtain black precipitate, pouring out supernatant, pyrolyzing the black precipitate and residual biological cells together at 400 ℃ for 2 hours, and obtaining the transition metal doped ferro-manganese composite oxide labeled as Bio-FeMnCeO after pyrolysis x 。
Example 5
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in a constant temperature gas bath shaker at 165rpm and 30 deg.C for 2 days, and continuously adding 120mg/L transition metal Co to the culture medium 2+ And Cu 2+ The solution is cultured for 5 days;
(2) Standing and precipitating the culture medium after culturing in the step (1) to obtain black precipitate, pouring out supernatant, pyrolyzing the black precipitate and residual biological cells together at 400 ℃ for 2 hours, and obtaining the transition metal doped ferro-manganese composite oxide labeled as Bio-FeMnCoCuO after pyrolysis x 。
Example 6
Preparation of 5 portions of 100ml moxifloxacin solution with concentration of 20mg/LThe pH was adjusted to 7.0 in a liquid and conical flask, 2ml of PMS was added at a concentration of 4g/L, and 3mg of Bio-FeMnCoO prepared in example 1-example 5, respectively, was added x 、Bio-FeMnNiO x 、Bio-FeMnCuO x Bio-FeMnCeO x And Bio-FeMnCoCuO x Placing 5 conical flasks in a constant temperature water bath kettle, sampling at 25 ℃ at intervals of 1min, 3min, 5min, 7min, 10min, 15min and 20min, filtering with 0.45 μm filter membrane, and measuring the residual concentration of moxifloxacin at different times by HPLC.
The test results are shown in fig. 1, and the results show that: the biological iron-manganese-cobalt composite oxide has the best catalytic effect, wherein the effect of doping transition metal Co in doping one transition metal is the best, and the effect of doping two transition metals Co and Cu is not remarkably increased compared with the effect of doping only one Co.
The invention will be further described below by taking biological iron-manganese-cobalt mixed oxide as an example.
Example 7
The biological iron-manganese-cobalt composite oxide prepared in the embodiment 2 is subjected to X-ray photoelectron spectroscopy (XPS) characterization, and the Mn 2p spectrum is shown in fig. 2.
As can be seen from fig. 2: the biological iron-manganese-cobalt composite oxide contains rich metal valence, is favorable for electron transfer and generates active group to degrade MOX.
Example 8
2 portions of 100ml of moxifloxacin solution with the concentration of 20mg/L are prepared, the pH value is adjusted to 7.0 in a conical flask, 2ml of PMS with the concentration of 4g/L is added, and 3mg of Ch-FeMnCoO is respectively added x And Bio-FeMnCoO prepared in example 2 x The rest of the procedure is the same as in example 6, ch-FeMnCoO x The method is a chemical iron-manganese-cobalt composite oxide, and the effect of different synthesis modes of the iron-manganese-cobalt composite oxide on the degradation of moxifloxacin by activated peroxymonosulfate is tested.
The test results are shown in fig. 3, and the results indicate that: biological Fe-Mn-Co composite oxide Bio-FeMnCoO x The effect of degrading moxifloxacin is that the chemical iron-manganese-cobalt composite oxide Ch-FeMnCoO x Is 6 times as large as that of the above.
Example 9
A biological preparation method of transition metal doped iron-manganese composite oxide comprises the following steps:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Culturing in 8 parts of culture medium, placing in a constant temperature gas bath table at 165rpm, setting the culture temperature to 30deg.C, culturing for 2 days, and continuously adding a certain amount of cobalt nitrate solution to the culture medium to make Co after adding 2+ The concentrations are respectively 0mg/L, 10mg/L, 20mg/L, 40mg/L, 80mg/L, 120mg/L, 160mg/L and 200mg/L, and the culture is continued for 5 days;
(2) Standing and precipitating the culture medium after the culturing in the step (1), pouring out supernatant, standing and pouring out supernatant, and then pyrolyzing metal oxide and residual biological cells together at 400 ℃ for 2 hours, wherein the metal oxide and residual biological cells are respectively marked as Co-0, co-10, co-20, co-40, co-80, co-120, co-160 and Co-200.
8 parts of a moxifloxacin solution with the concentration of 20mg/L and 100ml is prepared, the pH value is regulated to 7.0, 2ml of PMS with the concentration of 4g/L is added, 3mg of prepared Co-0, co-10, co-20, co-40, co-80, co-120, co-160 and Co-200 are respectively added, and the other steps are the same as those of example 5, so that the removal effect of the activated peroxymonosulfate for degrading the moxifloxacin by using different cobalt addition amounts on the biological iron-manganese-cobalt composite oxide is tested.
As shown in FIG. 4, the effect of the biological iron-manganese-cobalt composite oxide is 28 times of that of the biological iron-manganese oxide when the cobalt doping amount is 120mg/L, and the cobalt doping can improve the reaction rate, reduce the reaction time and reduce the operation cost.
The invention inoculates Pseudomonas sp.F2 strain into the strain containing Fe 2+ And Mn of 2+ The biological ferromanganese oxide can be obtained by culturing in a culture medium, transition metal ions are added after culturing for 1-3 days, the metal ions are oxidized into high-valence oxides by utilizing the biological activity and the growth metabolism process of Pseudomonas sp.F2, and meanwhile, the biological ferromanganese oxide is used as a carrier to oxidize and adsorb the metal ions on the surface of the biological ferromanganese oxide, so that the biological ferromanganese composite oxide doped with the transition metal ions is obtained. The biological iron-manganese composite oxide is used for activating the peroxymonosulfate, SO that the peroxymonosulfate can be efficiently activated to generate SO 4 - Sum of 1 O 2 The moxifloxacin in water is degraded, and the potential harm to the environment and human is reduced.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (5)
1. The biological preparation method of the transition metal doped ferro-manganese composite oxide is characterized by comprising the following steps of:
(1) Inoculating Pseudomonas putida sp.F2 under aseptic condition to Fe-containing strain 2+ And Mn of 2+ Placing the culture medium in a constant temperature gas bath table, setting the culture temperature at 165rpm, continuously adding a transition metal solution into the culture medium after culturing for 1-3 days, and continuously culturing for 4-10 days;
(2) Standing and precipitating the culture medium after the culture in the step (1) to obtain black precipitate, pouring out supernatant, performing pyrolysis on the black precipitate and residual biological cells together, setting pyrolysis temperature and pyrolysis time, and performing pyrolysis to obtain the transition metal doped iron-manganese composite oxide;
the culture medium in the step (1) contains Fe 2+ The concentration is 100-1000 mg/L, mn 2+ The concentration is 20-100 mg/L, and Fe in the culture medium 2+ ：Mn 2+ The concentration ratio is 5-10: 1, a step of;
the transition metal solution in step (1) contains Co 2+ 、Cu 2+ 、Ni 2+ And Ce (Ce) 2+ Any one or more metal ions;
the concentration of metal ions in the transition metal solution in the step (1) is 0.02-1.0 g/L;
the pyrolysis temperature in the step (2) is 200 ℃, 400 ℃ or 600 ℃ and the pyrolysis time is 2h.
2. The biological preparation method of the transition metal doped ferromanganese composite oxide according to claim 1, wherein the culture temperature in the step (1) is 20-40 ℃.
3. The biological preparation method of the transition metal doped iron-manganese composite oxide according to claim 1, wherein the medium composition in the step (1) comprises: peptone with final concentration of 1290mg/L, yeast extract powder with final concentration of 320mg/L, K with final concentration of 240mg/L 2 HPO 4 •3H 2 MgSO of O, 320mg/L 4 •7H 2 O, 240mg/L CaCl 2 •2H 2 O, 120mg/L NaNO 3 NH of 150mg/L 4 Cl。
4. A transition metal-doped iron-manganese composite oxide prepared by the biological preparation method of a transition metal-doped iron-manganese composite oxide according to any one of claims 1 to 3.
5. Use of the transition metal doped iron-manganese composite oxide according to claim 4 for treating moxifloxacin in sewage.
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