CN115739023B - Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof - Google Patents
Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 38
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 244000005700 microbiome Species 0.000 claims abstract description 21
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- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 6
- 238000008416 Ferritin Methods 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 102000008857 Ferritin Human genes 0.000 claims description 42
- 108050000784 Ferritin Proteins 0.000 claims description 42
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 241000863430 Shewanella Species 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 28
- 239000001963 growth medium Substances 0.000 claims description 26
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- 238000012258 culturing Methods 0.000 claims description 22
- 108090000623 proteins and genes Proteins 0.000 claims description 21
- -1 ferrous amine salt Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000411 inducer Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 14
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical group [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 9
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 230000001939 inductive effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
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- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims description 4
- 239000013612 plasmid Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 79
- 230000003197 catalytic effect Effects 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 230000001580 bacterial effect Effects 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000012452 mother liquor Substances 0.000 description 17
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- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
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- 239000012299 nitrogen atmosphere Substances 0.000 description 6
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- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 239000012137 tryptone Substances 0.000 description 5
- 239000012138 yeast extract Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
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- 238000001994 activation Methods 0.000 description 3
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- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001115170 Pyrococcus furiosus DSM 3638 Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 102000034238 globular proteins Human genes 0.000 description 1
- 108091005896 globular proteins Proteins 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microorganism enrichment. Compared with the prior art, the preparation method of the biological carbon adopts a one-step method, prepares the porous heterogeneous element doped loaded high-dispersion nano Fe composite material through biological reduction and simple chemical activation, has the advantages of higher specific surface area, rich pore structure, low cost, good adsorption performance, high catalytic activity, good stability and the like, is a novel biological carbon material, can induce persulfate activator with high efficiency and low cost to generate enough amount of oxidation active substances to realize the efficient degradation of organic pollutants, particularly obviously improves the capability of degrading bisphenol A, has good recycling performance and can be recycled for multiple times.
Description
Technical Field
The invention belongs to the technical field of water treatment and environmental catalysis, and particularly relates to an iron-nitrogen co-doped biological carbon material based on microorganism enrichment, a preparation method and application thereof.
Background
Advanced oxidation processes based on persulfates play an increasing role in the field of environmental protection, including degradation of refractory organics in water, disinfection, decomposition of activated sludge, and the like. Compared with the advanced oxidation technology represented by the typical Fenton technology, the persulfate has the characteristics of more positive reduction potential, pH independent reactivity, higher oxidation selectivity, longer service life and the like.
Persulfate advanced oxidation technology generates sulfate radical (·so) mainly by activating persulfate 4 - ) Active substances such as hydroxyl radicals (OH) and strong oxidative non-radicals, and the like, thereby realizing efficient degradation of pollutants. However, the catalyst for activating persulfate generally has the problems of high cost, poor performance, difficult recycling and the like. Meanwhile, the persulfate activation process and the types of active substances generated are affected by environmental conditions such as solution pH, coexisting ions and Natural Organic Matter (NOM), but the specific influence mechanism is not known. Non-radical contaminant degradation pathways are increasingly gaining attention due to higher selectivity for target contaminants and better environmental flexibility than radical pathways. Therefore, intensive research into the generation of active substances and response mechanisms to environmental conditions will help to further promote the practical application of sulfate advanced oxidation systems.
The non-free radical system has selectivity and relatively high reactivity to the electron-rich compound, so that the reaction rate with natural organic matters is low, and the method is favorable for treating natural water and trace organic pollutants. And the non-free matrix system is hardly influenced by anions in water, can adapt to various pH conditions, and is safer than a free radical way. At present, sludge-based biochar catalysts are often used for activating persulfates to realize non-radical route degradation, but biochemical sludge from different sources may have differences in specific components, and the catalytic effect is adversely affected.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide an iron-nitrogen co-doped biochar material based on microorganism enrichment, a preparation method and application thereof, and the iron-nitrogen co-doped biochar material has good adsorption performance, high catalytic activity and good stability.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microorganism enrichment, which comprises the following steps:
s1) culturing Shewanella engineering bacteria carrying ferritin encoding genes, adding ferrous salt containing nitrogen elements for continuous culture after ferritin expression is induced, and obtaining iron-rich bacteria;
s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism-enriched iron-nitrogen co-doped biochar material.
Preferably, the Shewanella engineering bacterium carrying ferritin encoding genes is prepared according to the following method:
the plasmid pYDT-ferritin is transformed into Shewanella to obtain Shewanella engineering bacteria carrying ferritin encoding genes.
Preferably, the Shewanella is MR-1 Shewanella.
Preferably, the culture medium used for culturing the Shewanella engineering bacterium carrying the ferritin encoding gene in the step S1) is a 2 XYT culture medium;
inducing ferritin expression by using arabinose as an inducer;
the ferrous salt containing nitrogen element is ferrous ammonium sulfate and/or ferrous glycinate.
Preferably, in the step S1), shewanella engineering bacteria carrying ferritin encoding genes are cultured until the OD600 of the culture solution is 0.4-0.6;
adding an inducer to induce ferritin expression; the addition amount of the inducer ensures that the concentration of the inducer in the culture solution is 0.001-0.01 mol/L; the time for inducing the expression of ferritin is 20-50 min;
the adding amount of the ferrous salt containing nitrogen element ensures that the concentration of ferrous amine salt in the culture solution is 0.001-0.005 mol/L;
the continuous culture time is 15-30 h.
Preferably, the alkaline substance is selected from alkali metal hydroxides; the mass ratio of the iron-rich bacteria to the alkaline substances is 1: (0.5-1.5).
Preferably, the calcination temperature is 300-600 ℃; the calcination time is 1-4 h; the temperature rising rate of the calcination is 3-8 ℃/min.
The invention also provides the Fe-N co-doped biological carbon material based on the microbial enrichment, which is prepared by the preparation method.
The invention also provides an application of the Fe-N co-doped biochar material based on microbial enrichment as a persulfate activator.
The invention also provides a degradation method of the organic pollutants in the water body, which comprises the following steps:
the iron-nitrogen co-doped biological carbon material based on microorganism enrichment prepared by the preparation method is used as a catalyst, persulfate is used as an oxidant, and the water body containing organic pollutants is treated.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microorganism enrichment, which comprises the following steps: s1) culturing Shewanella engineering bacteria carrying ferritin encoding genes, adding ferrous salt containing nitrogen elements for continuous culture after ferritin expression is induced, and obtaining iron-rich bacteria; s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism-enriched iron-nitrogen co-doped biochar material. Compared with the prior art, the preparation method of the biological carbon adopts a one-step method, prepares the porous heterogeneous element doped loaded high-dispersion nano Fe composite material through biological reduction and simple chemical activation, has the advantages of higher specific surface area, rich pore structure, low cost, good adsorption performance, high catalytic activity, good stability and the like, is a novel biological carbon material, can induce persulfate activator with high efficiency and low cost to generate enough amount of oxidation active substances to realize the efficient degradation of organic pollutants, particularly obviously improves the capability of degrading bisphenol A, has good recycling performance, can be recycled for multiple times, has great advantages in the aspect of removing organic pollutants in water body, and has high use value and good application prospect; the invention realizes the wide application from basic biology to environmental problems by programming and utilizing the cells of organisms and by means of a synthetic biology tool, firstly utilizes the microorganism to enrich the iron element in the culture medium in situ and prepare the biological carbon material, and uses the mode microorganism Shewanella as a miniature factory for green synthesis of nano Fe. The Shewanella adopted is easy to culture, the technical cost is low, the preparation method is simple, and the method is economical and environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope image of the biochar material obtained in example 1 and comparative example 1 of the present invention;
FIG. 2 is a graph showing degradation power of bisphenol A by the biochar materials obtained in example 1, comparative example 2 and comparative example 3 according to the present invention;
FIG. 3 is a graph showing the degradation kinetics of the biochar material obtained in example 1 of the present invention with respect to bisphenol A at different pH values;
FIG. 4 is a graph showing the degradation kinetics of the bio-carbon material obtained in example 1 of the present invention on bisphenol A by repeatedly activating a potassium hydrogen peroxymonosulfate complex salt;
FIG. 5 is a graph showing the degradation kinetics of the bio-carbon material obtained in example 1 of the present invention to bisphenol A at different amounts of bio-carbon material;
FIG. 6 is a graph showing the degradation kinetics of the biochar material obtained in example 1 of the present invention against bisphenol A at different amounts of potassium hydrogen peroxymonosulfate compound salt oxidizer;
FIG. 7 is a graph showing the degradation kinetics of bisphenol A by the biochar material obtained in example 2 of the present invention;
FIG. 8 is a graph showing the degradation kinetics of bisphenol A by the biochar material obtained in example 3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microorganism enrichment, which comprises the following steps: s1) culturing Shewanella engineering bacteria carrying ferritin encoding genes, adding ferrous salt containing nitrogen elements for continuous culture after ferritin expression is induced, and obtaining iron-rich bacteria; s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism-enriched iron-nitrogen co-doped biochar material.
Ferritin is present in almost all organisms and is a globular protein complex capable of forming hollow nanocages of various metal-protein interactions. Within the ferritin shell, the iron ions form crystallites together with phosphate and hydroxide ions, the resulting particles being similar to mineral ferrihydrite. The biological enrichment effect exists in the organism, the protein can be combined with isolated metal ions, and the uptake of the metal ions can promote the formation of the protein, so that the coordinated metal ions can be positioned in the organism. The ferrous ammonium salt is used as an iron source for microbial cultivation, and in the growth process, iron ions in the Shewanella enrichment culture medium are in ferritin, so that the aim of artificially and controllably enriching iron elements is fulfilled, and then bacteria are directly carbonized and activated, so that the iron-nitrogen co-doped biological carbon material can be obtained, and further the iron-nitrogen co-doped biological carbon material can be applied to the field of environmental catalysis.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
In the present invention, the Shewanella engineering bacterium carrying ferritin encoding gene is preferably prepared according to the following method: the plasmid pYDT-ferritin is transformed into Shewanella to obtain Shewanella engineering bacteria carrying ferritin encoding genes. The plasmid pYYDT-ferritin is formed by connecting a gene encoding ferritin with a vector pYDT; the Shewanella is preferably MR-1 Shewanella.
Culturing Shewanella engineering bacteria carrying ferritin encoding genes; the cultivation is preferably carried out in a liquid medium; the liquid medium is preferably a 2 XYT medium; the formula of the 2 XYT culture medium is specifically Tryptone 16g/L Yeast Extract 10g/L NaCl 5g/L; the inoculation amount is preferably 1% -2%; the cultivation is preferably carried out in a constant temperature shaker; the rotation speed of the culture is preferably 150 to 300rpm, more preferably 200 to 250rpm, still more preferably 220rpm; the temperature of the culture is preferably 25℃to 35℃and more preferably 30 ℃; in the present invention, shewanella engineering bacteria carrying ferritin encoding genes are preferably cultured until the OD600 of the culture solution is 0.4 to 0.6, more preferably 0.42 to 0.55, still more preferably 0.45 to 0.5; in the examples provided herein, the OD600 of the culture broth for the Shewanella engineering bacterium harboring the ferritin encoding gene was specifically 0.475 or 0.432.
Then inducing ferritin expression; in the present invention, it is preferable to add an inducer to induce ferritin expression; the inducer is preferably arabinose; the inducer is preferably added in an amount such that the concentration of the inducer in the culture solution is 0.001 to 0.01mol/L, more preferably 0.003 to 0.008mol/L, still more preferably 0.004 to 0.006mol/L, and most preferably 0.005mol/L; the inducer is preferably added in the form of an aqueous inducer solution; the concentration of the inducer aqueous solution is preferably 0.5 to 2mol/L, more preferably 0.8 to 1.5mol/L, still more preferably 1mol/L; the time for inducing ferritin expression is preferably 20 to 50 minutes, more preferably 30 to 40 minutes.
Adding ferrous salt containing nitrogen element for continuous culture; the ferrous salt containing nitrogen element is ferrous ammonium sulfate and/or ferrous glycinate; the amount of the nitrogen-containing ferrite to be added is preferably such that the concentration of the nitrogen-containing ferrite in the culture solution is 0.001 to 0.005mol/L, more preferably 0.002 to 0.004mol/L, still more preferably 0.002 to 0.003mol/L, most preferably 0.002 to 0.0025mol/L; the time for continuing the culture is preferably 15 to 30 hours, more preferably 18 to 28 hours, still more preferably 20 to 26 hours, and most preferably 24 hours.
After the continuous culture is finished, preferably centrifuging, washing, drying and grinding to obtain iron-rich bacteria; the rotational speed of the centrifugation is preferably 5000 to 10000rpm, more preferably 7000 to 9000rpm, still more preferably 8000rpm; the centrifugation time is preferably 1 to 10min, more preferably 3 to 8min, and still more preferably 5min; the washing is preferably carried out by adopting Tris-HCl solution and deionized water in sequence; the concentration of the Tris-HCl solution is preferably 10 to 30mM, more preferably 15 to 25mM, still more preferably 20mM; the pH value of the Tris-HCl solution is preferably 6-7, more preferably 6.5-7, and still more preferably 6.8; the drying temperature is preferably 100-120 ℃, more preferably 100-110 ℃, and still more preferably 105 ℃; the drying time is preferably 20 to 30 hours, more preferably 22 to 26 hours, still more preferably 24 hours.
Mixing the iron-rich bacteria with an alkaline substance, and calcining in a protective atmosphere; the alkaline substance is preferably an alkali metal hydroxide, more preferably potassium hydroxide and/or sodium hydroxide, still more preferably potassium hydroxide; the mass ratio of the iron-rich bacteria to the alkaline substance is preferably 1: (0.5 to 1.5), more preferably 1: (0.5 to 1.2), and more preferably 1: (0.5-1); the protective atmosphere is a protective atmosphere well known to those skilled in the art, and is not particularly limited, and nitrogen is preferred in the present invention; the calcination temperature is preferably 300-600 ℃, more preferably 350-500 ℃, and still more preferably 400-450 ℃; the calcination time is preferably 1 to 4 hours, more preferably 2 to 3 hours; the heating rate of the calcination is preferably 3-8 ℃/min, more preferably 4-6 ℃/min, and still more preferably 5 ℃/min; preferably, the calcined product is naturally cooled to room temperature.
Preferably washing after cooling to room temperature, and drying to obtain the Fe-N co-doped biological carbon material based on microorganism enrichment; the washing is preferably performed by hydrochloric acid and deionized water, more preferably by hydrochloric acid and deionized water for 2-4 times, so as to remove alkali and chloride ion residues; the concentration of the hydrochloric acid is preferably 0.4 to 1mol/L, more preferably 0.5 to 0.8mol/L, still more preferably 0.6mol/L; the drying temperature is preferably 60 to 80 ℃, more preferably 65 to 70 ℃.
The preparation method adopts a one-step biological carbon preparation method, prepares the porous heterogeneous element doped loaded high-dispersion nano Fe composite material through biological reduction and simple chemical activation, has the advantages of higher specific surface area, rich pore structure, low cost, good adsorption performance, high catalytic activity, good stability and the like, is a novel biological carbon material, can induce persulfate activator with high efficiency and low cost to generate enough amount of oxidation active substances to realize the efficient degradation of organic pollutants, particularly obviously improves the capability of degrading bisphenol A, has good recycling performance, can be recycled for multiple times, has great advantages in the aspect of removing the organic pollutants of water body, and has high use value and good application prospect; the invention realizes the wide application from basic biology to environmental problems by programming and utilizing the cells of organisms and by means of a synthetic biology tool, firstly utilizes the microorganism to enrich the iron element in the culture medium in situ and prepare the biological carbon material, and uses the mode microorganism Shewanella as a miniature factory for green synthesis of nano Fe. The Shewanella adopted is easy to culture, the technical cost is low, the preparation method is simple, and the method is economical and environment-friendly.
The invention also provides the Fe-N co-doped biological carbon material based on the microbial enrichment, which is prepared by the method.
The invention also provides an application of the iron-nitrogen co-doped biochar material based on microorganism enrichment as a persulfate activator.
The invention also provides a degradation method of the organic pollutants in the water body, which comprises the following steps: the iron-nitrogen co-doped biological carbon material based on microorganism enrichment prepared by the preparation method is used as a catalyst, persulfate is used as an oxidant, and water containing organic pollutants is treated.
The persulfate is a persulfate well known to those skilled in the art, and is not particularly limited, and potassium hydrogen peroxymonosulfate complex salts are preferred in the present invention; the mass ratio of the Fe-N co-doped biological carbon material based on the microbial enrichment to the persulfate is preferably (1-3): 1, more preferably (1.5 to 2.5): 1, more preferably (1.8 to 2.2): 1, most preferably 2:1, a step of; the dosage of the Fe-N co-doped biological carbon material based on the microbial enrichment is preferably 0.02-1 g/L, more preferably 0.1-0.6 g/L, and still more preferably 0.2-0.4 g/L; the organic contaminant is not particularly limited as long as it is an organic contaminant well known to those skilled in the art, and bisphenol organic contaminants are preferable in the present invention, and bisphenol a is more preferable; the content of organic pollutants in the water body containing the organic pollutants is preferably less than or equal to 20mg/L; the treatment is preferably carried out under stirring at room temperature; the rotation speed of the stirring is preferably 200 to 600rpm, more preferably 300 to 500rpm, still more preferably 400rpm.
The degradation method of the organic pollutants in the water body has the advantages of simplicity in operation, high degradation efficiency, short operation period and the like, and can be used for efficiently degrading the organic pollutants in the water body.
In order to further illustrate the invention, the following examples are provided to describe a microorganism-enriched iron-nitrogen co-doped biochar material, a preparation method and application thereof in detail.
The reagents used in the examples below are all commercially available; the chassis strain of the engineering strain pYYDT-ferritin used in the examples and comparative examples is the wild type strain MR-1, the vector is pYDT, and the gene fragment is ferritin from Pyrococcus furiosus DSM 3638.
Example 1
Preparing liquid culture medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, packaging 500mL into 1000mL conical flask, and sterilizing with high pressure steam at 121deg.C for 20min; preparing ferrous ammonium sulfate mother liquor with the concentration of 0.5M, and removing bacteria through a 0.22 mu M filter membrane; and (3) inoculating the engineering strain pYYDT-ferritin into a liquid culture medium in an ultra-clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃, adding 2.5mL of 1M arabinose mother liquor for culturing for 30 minutes when the bacterial liquid concentration reaches OD600 = 0.475, adding 2.0mL of ferrous ammonium sulfate mother liquor, culturing for 24 hours, centrifuging at 8000rpm for 5 minutes, collecting bacterial liquid, washing with 20mM Tris-HCl with pH of 6.8 and deionized water once, drying in a 105 ℃ oven for 24 hours, and grinding to obtain dry iron-rich bacterial powder. Transferring the mixed mass ratio of the iron-rich bacterial powder and KOH to a corundum crucible at 1:1, placing the corundum crucible in a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature at the gas flow rate of 20mL/min, calcining under the nitrogen atmosphere at the heating rate of 5 ℃/min, the calcining temperature of 400 ℃ for 2 hours, and naturally cooling to room temperature to obtain a solid biological carbon material; washing the obtained biochar material with 0.6M hydrochloric acid and deionized water three times respectively, removing alkali and chloride ion residues, and drying in oven at 65deg.C to obtain biochar material, designated as Fe-BC Ferritin 。
Comparative example 1
Liquid culture medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) was prepared with distilled water, and 500mL was dispensed into 1000mL conesSterilizing in a bottle with high pressure steam at 121deg.C for 20min; preparing ferrous ammonium sulfate mother liquor with the concentration of 0.5M, and removing bacteria through a 0.22 mu M filter membrane; and (3) inoculating the engineering strain pYYDT-ferritin into a liquid culture medium in an ultra-clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃, adding 2.5mL of 1M arabinose mother liquor when the concentration of the bacterial liquid reaches OD600 = 0.424, culturing for 24 hours without adding ferrous ammonium sulfate solution, centrifuging at 8000rpm for 5min to collect bacterial liquid, washing with 20mM Tris-HCl with pH of 6.8 and deionized water once, drying in a 105 ℃ oven for 24 hours, and grinding to obtain dry bacterial powder. Transferring the bacterial powder and KOH into a corundum crucible in a mass ratio of 1:1, placing the corundum crucible into a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature, calcining under the nitrogen atmosphere at a temperature rising rate of 5 ℃/min and a calcining temperature of 400 ℃ for 2 hours, and naturally cooling to room temperature to obtain a solid biological carbon material; washing the obtained biochar material with 0.6M hydrochloric acid and deionized water three times respectively, removing alkali and chloride ion residues, and drying in oven at 65deg.C to obtain biochar material named BC Ferritin 。
Comparative example 2
Preparing liquid culture medium 2 XYT with distilled water, packaging 500mL in 1000mL conical flask, and sterilizing with high pressure steam at 121deg.C for 20min; preparing ferrous ammonium sulfate mother liquor with the concentration of 0.5M, and removing bacteria through a 0.22 mu M filter membrane; the wild strain MR-1/WT is put into a liquid culture medium in an ultra-clean bench, the culture medium is placed in a constant temperature shaking table, and is cultured at 220rpm and 30 ℃, when the bacterial liquid concentration reaches OD600 = 0.503, 2.5mL of 1M arabinose mother liquor is added for 30 minutes, 2.0mL of ferrous ammonium sulfate mother liquor is added for culturing for 24 hours, centrifugation is carried out at 8000rpm for 5 minutes to collect bacterial liquid, and after washing with 20mM Tris-HCl with pH of 6.8 and deionized water, drying is carried out in an oven at 105 ℃ for 24 hours, and then grinding is carried out to obtain dry bacterial powder. Transferring the bacterial powder and KOH into a corundum crucible in a mass ratio of 1:1, placing the corundum crucible into a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature, wherein the gas flow rate is 20mL/min, calcining under nitrogen atmosphere, and the heating rate is 5 ℃/min, and calcining at the temperatureThe temperature is 400 ℃, the calcination time is 2 hours, and the solid biological carbon material is obtained after natural cooling to room temperature; washing the obtained biochar material with 0.6M hydrochloric acid and deionized water three times respectively, removing alkali and chloride ion residues, and drying in oven at 65deg.C to obtain biochar material, designated as Fe-BC WT 。
Comparative example 3
Preparing liquid culture medium 2 XYT with distilled water, packaging 500mL in 1000mL conical flask, and sterilizing with high pressure steam at 121deg.C for 20min; preparing ferrous ammonium sulfate mother liquor with the concentration of 0.5M, and removing bacteria through a 0.22 mu M filter membrane; the method comprises the steps of inoculating a wild strain MR-1/WT into a liquid culture medium in an ultra-clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃, adding 2.5mL of 1M arabinose mother liquor when the concentration of bacterial liquid reaches OD600 = 0.421, culturing for 24 hours without adding ferrous ammonium sulfate mother liquor, centrifuging at 8000rpm for 5 minutes to collect bacterial liquid, washing with 20mM Tris-HCl with pH of 6.8 and deionized water once, drying in a 105 ℃ oven for 24 hours, and grinding to obtain dry bacterial powder. Transferring the bacterial powder and KOH into a corundum crucible in a mass ratio of 1:1, placing the corundum crucible into a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature, calcining under the nitrogen atmosphere at a temperature rising rate of 5 ℃/min and a calcining temperature of 400 ℃ for 2 hours, and naturally cooling to room temperature to obtain a solid biological carbon material; washing the obtained biochar material with 0.6M hydrochloric acid and deionized water three times respectively, removing alkali and chloride ion residues, and drying in oven at 65deg.C to obtain biochar material named BC WT 。
The biochar materials obtained in example 1 and comparative example 1 were analyzed by scanning electron microscopy, and a scanning electron microscopy chart thereof was obtained as shown in fig. 1.
In order to examine the catalytic performance of the iron-nitrogen co-doped carbon biochar material prepared by the invention, the experiment is as follows: 30mL of 10mg/L bisphenol A solution was prepared, and 6mg of Fe-BC was added Ferritin Sample, BC Ferritin Sample, BC WT Sample and Fe-BC WT Sample, 3mg of potassium hydrogen peroxymonosulfate complex salt oxidizer. Sampling at regular time under the condition of room temperature and rotating speed of 400rpmThe concentration of bisphenol A in the solution is detected, and a degradation dynamic curve diagram of the biological carbon material on bisphenol A is shown in figure 2. Based on the measurement results, bisphenol A in the system can be completely removed within 10 min.
30mL of 10mg/L bisphenol A solution is prepared, the pH value of the solution is regulated to 4.0-10.0 by using HCl and NaOH, 6mg of Fe-BC sample and 3mg of potassium hydrogen peroxymonosulfate compound salt oxidant are added. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and rotating speed of 400rpm, and the degradation power curve graph of the biological carbon material on bisphenol A under different pH values is shown in figure 3.
30mL of 10mg/L bisphenol A solution was prepared, and 6mg of Fe-BC was added Ferritin Sample, 3mg of potassium hydrogen peroxymonosulfate complex salt oxidizer. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and 400rpm, after 30min, distilled water is filtered to wash Fe-BC sample, the operation is repeated, and the degradation power curve graph of the biological carbon material repeatedly activated potassium hydrogen peroxymonosulfate compound salt on bisphenol A is shown in figure 4.
Influence of the addition amount of the biochar material on the bisphenol A removal effect
30mL of 10mg/L bisphenol A solution was prepared, and 0.3g/L, 0.2g/L, 0.1g/L, 0.05g/L, and 0.02g/L of Fe-BC were added, respectively Ferritin The sample is added with 0.1g/L of potassium hydrogen peroxymonosulfate compound salt oxidant. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and rotating speed of 400rpm, and the degradation dynamics curve graph of bisphenol A under different adding amounts of the biological carbon materials is shown in figure 5.
As can be seen from FIG. 5, the removal rate of the biochar material gradually increased from 30% to 100% when the addition amount of the biochar material gradually increased from 0.02g/L to 0.3 g/L. The adding amount of the biological carbon material is increased, the provided adsorption area and active sites are also increased, and the bisphenol A removal efficiency is obviously improved.
Influence of addition amount of potassium hydrogen peroxymonosulfate composite salt oxidant on bisphenol A removal effect
30mL of 10mg/L bisphenol A solution was prepared, and 0.2g/L Fe-BC was added Ferritin The sample is respectively added with 0.2g/L, 0.1g/L, 0.05g/L and 0.02g/L of potassium hydrogen peroxymonosulfate compound salt oxidant. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and rotating speed of 400rpm, and the degradation kinetics curve graph of bisphenol A under different adding amounts of potassium hydrogen peroxymonosulfate compound salt oxidizing agent is shown in figure 6.
As can be seen from FIG. 6, with the increase of the addition amount of the potassium hydrogen peroxymonosulfate compound salt oxidant, the bisphenol A removal rate is significantly improved, and when the addition amount is 0.1g/L, the bisphenol A solution removal rate with the concentration of 10mg/L can reach 100%, thereby achieving a more ideal removal effect.
Example 2
Preparing liquid culture medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, packaging 500mL into 1000mL conical flask, and sterilizing with high pressure steam at 121deg.C for 20min; preparing ferrous ammonium sulfate mother liquor with the concentration of 0.5M, and removing bacteria through a 0.22 mu M filter membrane; and (3) inoculating the engineering strain pYYDT-ferritin into a liquid culture medium in an ultra-clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃, adding 2.5mL of 1M arabinose mother liquor for culturing for 30 minutes when the bacterial liquid concentration reaches OD600 = 0.432, adding 2.0mL of ferrous ammonium sulfate mother liquor, culturing for 24 hours, centrifuging at 8000rpm for 5 minutes, collecting bacterial liquid, washing with 20mM Tris-HCl with pH of 6.8 and deionized water once, drying in a 105 ℃ oven for 24 hours, and grinding to obtain dry iron-rich bacterial powder. Transferring the mixed bacterial powder rich in iron and KOH into a corundum crucible with the mass ratio of 1:0.5, placing the corundum crucible into a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature, wherein the gas flow rate is 20mL/min, calcining under the nitrogen atmosphere, the heating rate is 5 ℃/min, the calcining temperature is 400 ℃, the calcining time is 4h, and naturally cooling to room temperature to obtain a solid biological carbon material; the obtained biochar material was washed three times with 0.6M hydrochloric acid and deionized water, alkali and chloride ion residues were removed, and dried in an oven at 65 ℃ to obtain the biochar material, and in order to examine the catalytic performance of the iron-nitrogen co-doped carbon biochar material prepared in this example 2, the experiment was as follows: 30mL of a 10mg/L bisphenol A solution was prepared, and 6mg of the sample of this example 2, 3mg of potassium hydrogen peroxymonosulfate compound salt oxidizing agent was added. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and rotating speed of 400rpm, and the degradation power curve diagram of the biological carbon material on bisphenol A is shown in figure 7. According to the measurement result, bisphenol A in the system can be effectively removed within 30min, and the removal rate reaches 90% within 30 min.
Example 3
Preparing liquid culture medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, packaging 500mL into 1000mL conical flask, and sterilizing with high pressure steam at 121deg.C for 20min; preparing ferrous glycine mother liquor 0.5M, and removing bacteria through a 0.22 mu M filter membrane; and (3) inoculating the engineering strain pYYDT-ferritin into a liquid culture medium in an ultra-clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃, adding 2.5mL of 1M arabinose mother liquor for culturing for 30 minutes when the concentration of the bacterial liquid reaches OD600 = 0.432, adding 2.0mL of ferrous glycinate mother liquor, culturing for 24 hours, centrifuging at 8000rpm for 5 minutes, collecting bacterial liquid, washing with 20mM Tris-HCl with pH of 6.8 and deionized water once, drying in a 105 ℃ oven for 24 hours, and grinding to obtain dry iron-rich bacterial powder. Transferring the mixed mass ratio of the iron-rich bacterial powder and KOH to a corundum crucible at 1:1, placing the corundum crucible in a tube furnace, introducing inert gas nitrogen into the tube furnace at room temperature at the gas flow rate of 20mL/min, calcining under the nitrogen atmosphere at the heating rate of 5 ℃/min, the calcining temperature of 400 ℃ for 2 hours, and naturally cooling to room temperature to obtain a solid biological carbon material; the obtained biochar material was washed three times with 0.6M hydrochloric acid and deionized water, alkali and chloride ion residues were removed, and dried in an oven at 65 ℃ to obtain the biochar material, and in order to examine the catalytic performance of the iron-nitrogen co-doped carbon biochar material prepared in this example 3, the experiment was as follows: 30mL of a 10mg/L bisphenol A solution was prepared, and 6mg of the sample of this example 2, 3mg of potassium hydrogen peroxymonosulfate compound salt oxidizing agent was added. The concentration of bisphenol A in the solution is detected by sampling at regular time under the conditions of room temperature and rotating speed of 400rpm, and the degradation power curve diagram of the biological carbon material on bisphenol A is shown in figure 8. According to the measurement result, bisphenol A in the system can be effectively removed within 30min, and the removal rate reaches 99% within 30 min.
Claims (10)
1. The preparation method of the Fe-N co-doped biochar material based on microorganism enrichment is characterized by comprising the following steps of:
s1) culturing Shewanella engineering bacteria carrying ferritin encoding genes, adding ferrous salt containing nitrogen elements for continuous culture after ferritin expression is induced, and obtaining iron-rich bacteria;
s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism-enriched iron-nitrogen co-doped biochar material.
2. The preparation method according to claim 1, wherein the Shewanella engineering bacterium carrying the ferritin encoding gene is prepared according to the following method:
the plasmid pYDT-ferritin is transformed into Shewanella to obtain Shewanella engineering bacteria carrying ferritin encoding genes.
3. The method of claim 2, wherein the shiva is MR-1 shiva.
4. The method according to claim 1, wherein the culture medium used for culturing the Shewanella engineering bacterium carrying the ferritin encoding gene in the step S1) is a 2 XYT culture medium;
inducing ferritin expression by using arabinose as an inducer;
the ferrous salt containing nitrogen element is ferrous ammonium sulfate and/or ferrous glycinate.
5. The method according to claim 1, wherein the OD600 of the culture solution obtained by culturing the shiva engineering bacterium carrying the ferritin encoding gene in step S1) is 0.4 to 0.6;
adding an inducer to induce ferritin expression; the addition amount of the inducer ensures that the concentration of the inducer in the culture solution is 0.001-0.01 mol/L; the time for inducing the expression of ferritin is 20-50 min;
the adding amount of the ferrous salt containing nitrogen element ensures that the concentration of ferrous amine salt in the culture solution is 0.001-0.005 mol/L;
the continuous culture time is 15-30 h.
6. The method according to claim 1, wherein the alkaline substance is selected from alkali metal hydroxides; the mass ratio of the iron-rich bacteria to the alkaline substances is 1: (0.5-1.5).
7. The method of claim 1, wherein the calcination temperature is 300 ℃ to 600 ℃; the calcination time is 1-4 h; the temperature rising rate of the calcination is 3-8 ℃/min.
8. An iron-nitrogen co-doped biochar material based on microbial enrichment prepared by the preparation method of any one of claims 1 to 7.
9. Use of the iron-nitrogen co-doped biochar material based on microbial enrichment prepared by the preparation method according to any one of claims 1 to 7 as persulfate activator.
10. The degradation method of the organic pollutants in the water body is characterized by comprising the following steps of:
the method for treating the water body containing the organic pollutants by using the iron-nitrogen co-doped biological carbon material based on microorganism enrichment prepared by the preparation method of any one of claims 1 to 7 as a catalyst and persulfate as an oxidant.
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