CN115739023A - 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
- Publication number
- CN115739023A CN115739023A CN202211510117.5A CN202211510117A CN115739023A CN 115739023 A CN115739023 A CN 115739023A CN 202211510117 A CN202211510117 A CN 202211510117A CN 115739023 A CN115739023 A CN 115739023A
- Authority
- CN
- China
- Prior art keywords
- iron
- ferritin
- nitrogen
- shewanella
- biological carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 44
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000000813 microbial effect Effects 0.000 title claims abstract description 16
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 52
- 238000008416 Ferritin Methods 0.000 claims description 47
- 241000894006 Bacteria Species 0.000 claims description 40
- 102000008857 Ferritin Human genes 0.000 claims description 38
- 108050000784 Ferritin Proteins 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 241000863430 Shewanella Species 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000001963 growth medium Substances 0.000 claims description 23
- 108090000623 proteins and genes Proteins 0.000 claims description 22
- 238000012258 culturing Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000411 inducer Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 13
- 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
- 244000005700 microbiome Species 0.000 claims description 13
- 230000001590 oxidative effect Effects 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 12
- 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
- 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
- -1 ferrous amine salt Chemical class 0.000 claims description 7
- 230000001939 inductive effect Effects 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002609 medium Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 239000013612 plasmid Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000001131 transforming effect Effects 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
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 238000006731 degradation reaction Methods 0.000 abstract description 24
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 230000001580 bacterial effect Effects 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 239000012452 mother liquor Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 239000012425 OXONE® Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 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
- 238000009630 liquid culture Methods 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
- 239000012153 distilled water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 229940041514 candida albicans extract Drugs 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000012137 tryptone Substances 0.000 description 5
- 239000012138 yeast extract Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 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
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 102000034238 globular proteins Human genes 0.000 description 1
- 108091005896 globular proteins Proteins 0.000 description 1
- 239000011261 inert gas Substances 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
- 238000009629 microbiological culture Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 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
- 231100000719 pollutant Toxicity 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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 microbial enrichment. Compared with the prior art, the invention adopts a one-step biological carbon preparation method, prepares the porous heterogeneous element doped and loaded composite material of high-dispersion nano Fe by biological reduction and simple and direct chemical activation, has higher specific surface area and abundant pore structures, has the advantages of low cost, good adsorption property, high catalytic activity, good stability and the like, is a novel biological carbon material, can efficiently induce persulfate activating agents with low cost to generate enough oxidation active substances to realize high-efficiency degradation of organic pollutants, particularly remarkably improves the capacity 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 microbial enrichment, and a preparation method and application thereof.
Background
The persulfate-based advanced oxidation process plays more and more roles in the field of environmental protection, including degradation and disinfection of refractory organic matters in water, decomposition of activated sludge and the like. Compared with the advanced oxidation technology represented by a typical Fenton process, the persulfate has the characteristics of more positive reduction potential, reaction activity independent of pH, higher oxidation selectivity, longer service life and the like.
The persulfate advanced oxidation technology mainly generates sulfate radical (. SO) by activating persulfate 4 - ) And hydroxyl radicals (. OH), strongly oxidizing non-radicals and the like, thereby realizing efficient degradation of pollutants. However, the persulfate-activating catalysts generally have the problems of high cost, poor performance, difficulty in recycling and the like. Meanwhile, the persulfate activation process and the types of active substances generated by the persulfate activation process are influenced by the pH of the solution, coexisting ions, natural organic compounds (NOM) and other environmental conditions, but the specific influence mechanism is not clear. Compared to the free radical route, the non-free radical contaminant degradation route is increasingly receiving attention due to higher selectivity for target contaminants and better environmental suitability. Therefore, the intensive research on the generation of active substances and the response mechanism to environmental conditions can help further promote the practical application of the sulfate advanced oxidation system.
The non-free matrix system is selective and has relatively high reaction activity to electron-rich compounds, so that the reaction rate with natural organic matters is low, and the treatment of natural water and trace organic pollutants is facilitated. 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 approach. At present, the sludge-based biochar catalyst is commonly used for activating persulfate to realize non-radical route degradation, but biochemical sludge from different sources may have differences on specific components and have adverse effects on catalytic effects.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide an iron-nitrogen co-doped biological carbon material based on microorganism enrichment, and a preparation method and an application thereof.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microbial enrichment, which comprises the following steps:
s1) culturing Shewanella engineering bacteria carrying ferritin coding genes, inducing ferritin expression, and adding ferrous salt containing nitrogen to continue culturing to obtain iron-rich bacteria;
s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism enrichment-based iron-nitrogen co-doped biological carbon material.
Preferably, the Shewanella engineering bacteria carrying ferritin ferriritin coding genes are prepared according to the following method:
and (3) transforming the plasmid pYYDT-ferritin into Shewanella to obtain the Shewanella engineering bacteria carrying ferritin-ferritin coding genes.
Preferably, the Shewanella is MR-1 Shewanella.
Preferably, the culture medium used for culturing the Shewanella engineering bacteria carrying the ferritin ferriritin encoding gene in the step S1) is 2 XYT culture medium;
using arabinose as an inducer to induce ferritin expression;
the ferrous salt containing nitrogen element is ammonium ferrous sulfate and/or ferrous glycinate.
Preferably, the Shewanella engineering bacteria carrying ferritin ferriritin encoding gene is cultured in the step S1) until OD600 of the culture solution is 0.4-0.6;
adding an inducer to induce ferritin expression; the addition amount of the inducer enables the concentration of the inducer in the culture solution to be 0.001-0.01 mol/L; the time for inducing the ferritin expression is 20-50 min;
the addition amount of the ferrous salt containing nitrogen elements ensures that the concentration of the ferrous amine salt in the culture solution is 0.001-0.005 mol/L;
the continuous culture time is 15-30 h.
Preferably, the basic 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 calcining temperature is 300-600 ℃; the calcining time is 1-4 h; the temperature rise rate of the calcination is 3-8 ℃/min.
The invention also provides an iron-nitrogen co-doped biological carbon material prepared by the preparation method based on microbial enrichment.
The invention also provides an application of the iron-nitrogen co-doped biological carbon material prepared by the preparation method based on microbial enrichment as a persulfate activator.
The invention also provides a method for degrading organic pollutants in a water body, which comprises the following steps:
the iron-nitrogen co-doped biological carbon material prepared by the preparation method based on microbial enrichment is used as a catalyst, persulfate is used as an oxidant, and water containing organic pollutants is treated.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microbial enrichment, which comprises the following steps: s1) culturing Shewanella engineering bacteria carrying ferritin ferriritin coding genes, inducing ferritin expression, adding ferrous salt containing nitrogen elements, and continuing culturing to obtain iron-rich bacteria; s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the iron-nitrogen co-doped biological carbon material based on microorganism enrichment. Compared with the prior art, the invention adopts a one-step biological carbon preparation method, prepares the porous heterogeneous element doped and loaded composite material of high-dispersion nano Fe by biological reduction and simple and direct chemical activation, has higher specific surface area and abundant pore structures, has the advantages of low cost, good adsorption property, high catalytic activity, good stability and the like, is a novel biological carbon material, can efficiently induce persulfate activating agents with low cost to generate enough oxidation active substances to realize high-efficiency degradation of organic pollutants, particularly remarkably improves the capacity of degrading bisphenol A, has good recycling performance, can be recycled for many times, has great advantages in removing organic pollutants in water, 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 cells of organisms and by means of a synthetic biology tool, firstly utilizes the iron element in the microorganism in-situ enrichment culture medium and prepares a biological carbon material, and uses the model microorganism Shewanella as a micro factory for green synthesis of nano Fe. The adopted Shewanella is easy to culture, the technical cost is low, the preparation method is simple, and the Shewanella is economic and environment-friendly.
Drawings
FIG. 1 is a scanning electron micrograph of a biocarbon material obtained in example 1 of the present invention and comparative example 1;
FIG. 2 is a graph showing the degradation kinetics of bisphenol A by the biochar materials obtained in example 1, comparative example 2 and comparative example 3 of the present invention;
FIG. 3 is a graph showing the degradation kinetics of bisphenol A at different pH values of the biochar material obtained in example 1 of the present invention;
FIG. 4 is a graph showing the degradation kinetics of bisphenol A by repeated activation of potassium peroxymonosulfate complex salt with the biological carbon material obtained in example 1 of the present invention;
FIG. 5 is a graph showing the degradation kinetics of the biochar material obtained in example 1 of the present invention to bisphenol A at different dosages of the biochar material;
FIG. 6 is a graph showing the degradation kinetics of bisphenol A with different dosages of potassium monopersulfate complex salt as an oxidant for the biochar material obtained in example 1 of the present invention;
FIG. 7 is a graph showing the degradation kinetics of bisphenol A by the biocarbon material obtained in example 2 of the present invention;
FIG. 8 is a graph showing the degradation kinetics of bisphenol A by the biocarbon material obtained in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an iron-nitrogen co-doped biological carbon material based on microbial enrichment, which comprises the following steps: s1) culturing Shewanella engineering bacteria carrying ferritin coding genes, inducing ferritin expression, and adding ferrous salt containing nitrogen to continue culturing to obtain iron-rich bacteria; s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the iron-nitrogen co-doped biological carbon material based on microorganism enrichment.
Ferritin is present in almost all organisms, is a globular protein complex that can form hollow nanocages of various metal-protein interactions. Within the iron protein shell, iron ions form microcrystals with phosphate and hydroxide ions, and the resulting particles resemble mineral ferrihydrite. The biological enrichment effect exists in organisms, proteins can be combined with isolated metal ions, and the uptake of the metal ions can promote the formation of the proteins, so that the coordinated metal ions can be positioned in the organisms. Ferrous ammonium salt is used as an iron source for microbial culture, iron ions in a Shewanella enrichment culture medium are in ferritin during growth, so that the aim of artificially and controllably enriching iron elements is fulfilled, then bacteria are directly carbonized and activated to obtain the iron-nitrogen co-doped biological carbon material, and further the iron-nitrogen co-doped biological carbon material can be applied to the field of environmental catalysis.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
In the present invention, the Shewanella engineering bacterium carrying ferritin ferriritin-encoding gene is preferably prepared according to the following method: and (3) transforming the plasmid pYYDT-ferritin into Shewanella to obtain the Shewanella engineering bacteria carrying ferritin coding genes. The plasmid pYYDT-ferritin is formed by connecting a gene which codes ferritin with the vector pYYDT; the Shewanella is preferably MR-1 Shewanella.
Culturing Shewanella engineering bacteria carrying ferritin ferricin coding gene; the cultivation is preferably carried out in a liquid medium; the liquid culture medium is preferably 2 XYT culture 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 shaking table; the rotation speed of the culture is preferably 150-300 rpm, more preferably 200-250 rpm, and still more preferably 220rpm; the culture temperature is preferably 25-35 ℃, and more preferably 30 ℃; in the present invention, it is preferable to culture Shewanella engineering bacteria carrying a gene encoding ferritin 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 by the present invention, shewanella engineered bacteria carrying ferritin ferriritin encoding gene were cultured to culture broth with OD600 of 0.475 or 0.432.
Then, ferritin expression is induced; 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 such an amount 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 water solution is preferably 0.5-2 mol/L, more preferably 0.8-1.5 mol/L, and still more preferably 1mol/L; the time for inducing ferritin expression is preferably 20 to 50min, more preferably 30 to 40min.
Adding ferrous salt containing nitrogen element for continuous culture; the ferrous salt containing nitrogen element is ammonium ferrous sulfate and/or ferrous glycinate; the adding amount of the ferrous salt containing the nitrogen element is preferably that the concentration of the ferrous salt containing the nitrogen element in the culture solution is 0.001-0.005 mol/L, more preferably 0.002-0.004 mol/L, even more preferably 0.002-0.003 mol/L, and most preferably 0.002-0.0025 mol/L; the time for the continuous 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 rotating speed of the centrifugation is preferably 5000-10000 rpm, more preferably 7000-9000 rpm, and even more preferably 8000rpm; the time for centrifugation is preferably 1-10 min, more preferably 3-8 min, and still more preferably 5min; washing preferably sequentially by adopting a Tris-HCl solution and deionized water; the concentration of the Tris-HCl solution is preferably 10-30 mM, more preferably 15-25 mM, and 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 further preferably 105 ℃; the drying time is preferably 20 to 30 hours, more preferably 22 to 26 hours, and still more preferably 24 hours.
Mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere; the alkaline substance is preferably an alkali metal hydroxide, more preferably potassium hydroxide and/or sodium hydroxide, and 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 to 1); the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and nitrogen is preferred in the present invention; the calcination temperature is preferably 300-600 ℃, more preferably 350-500 ℃, and further preferably 400-450 ℃; the calcination time is preferably 1 to 4 hours, and more preferably 2 to 3 hours; the heating rate of the calcination is preferably 3-8 ℃/min, more preferably 4-6 ℃/min, and further preferably 5 ℃/min; after calcination, the mixture is preferably cooled naturally to room temperature.
Cooling to room temperature, preferably washing, and drying to obtain an iron-nitrogen co-doped biological carbon material based on microorganism enrichment; preferably, the washing is carried out by hydrochloric acid and deionized water, and more preferably, the washing is carried out by hydrochloric acid and deionized water for 2 to 4 times respectively so as to remove alkali and chloride ion residues; the concentration of the hydrochloric acid is preferably 0.4-1 mol/L, more preferably 0.5-0.8 mol/L, and still more preferably 0.6mol/L; the drying temperature is preferably 60 ℃ to 80 ℃, and more preferably 65 ℃ to 70 ℃.
The invention adopts a one-step biochar preparation method, prepares the porous heterogeneous element doped and loaded composite material of high-dispersion nano Fe by biological reduction and simple and direct chemical activation, has higher specific surface area and abundant pore structures, has the advantages of low cost, good adsorption performance, high catalytic activity, good stability and the like, is a novel biochar material, can efficiently induce persulfate activators with low cost to generate enough oxidation active substances to realize high-efficiency degradation of organic pollutants, particularly remarkably improves the capacity of degrading bisphenol A, has good recycling performance, can be recycled for many times, has great advantages in removing organic pollutants in water, 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 cells of organisms and by means of a synthetic biology tool, firstly utilizes the iron element in the microorganism in-situ enrichment culture medium and prepares a biological carbon material, and uses the model microorganism Shewanella as a micro factory for green synthesis of nano Fe. The adopted Shewanella is easy to culture, the technical cost is low, the preparation method is simple, and the Shewanella is economic and environment-friendly.
The invention also provides an iron-nitrogen co-doped biological carbon material prepared by the method based on microbial enrichment.
The invention also provides an application of the iron-nitrogen co-doped biological carbon material prepared by the method as a persulfate activator.
The invention also provides a method for degrading organic pollutants in water, which comprises the following steps: the iron-nitrogen co-doped biological carbon material prepared by the preparation method based on microbial enrichment 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 in the present invention, potassium monopersulfate complex salts are preferred; the mass ratio of the iron-nitrogen co-doped biological carbon material based on 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; the dosage of the iron-nitrogen co-doped biological carbon material based on 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 known to those skilled in the art, and in the present invention, bisphenol organic contaminants are preferred, and bisphenol a is more preferred; the content of the 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 with stirring at room temperature; the rotation speed of the stirring is preferably 200 to 600rpm, more preferably 300 to 500rpm, and still more preferably 400rpm.
The degradation method of the organic pollutants in the water body provided by the invention has the advantages of simple operation, high degradation efficiency, short operation period and the like, and can efficiently degrade the organic pollutants in the water body.
In order to further illustrate the present invention, the following describes in detail an iron-nitrogen co-doped biocarbon material based on microorganism enrichment, a preparation method thereof, and an application thereof, with reference to examples.
The reagents used in the following examples are all commercially available; the underpan strain of the engineered strain pYYDT-ferricin used in the examples and comparative examples was the wild-type strain MR-1, the vector was pYYDT and the gene fragment was ferricin from Pyrococcus furiosus DSM 3638.
Example 1
Preparing liquid medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, subpackaging 500mL in 1000mL conical flasks, and autoclaving at 121 ℃ for 20min; preparing 0.5M of ammonium ferrous sulfate mother liquor, and removing bacteria through a 0.22-micron filter membrane; the engineering strain pYYDT-ferritin is inoculated into a liquid culture medium in a super-clean bench, the culture medium is placed in a constant-temperature shaking table and cultured under the conditions of 220rpm and 30 ℃, when the concentration of bacterial liquid reaches OD600=0.475, 2.5mL of 1M arabinose mother liquor is added for culturing for 30 minutes, 2.0mL of ammonium ferrous sulfate mother liquor is added, after 24 hours of culture, the bacterial liquid is collected by centrifugation at 8000rpm for 5 minutes, and after being washed once by using 2 mM of Tris-HCl with pH =6.8 and deionized water, the bacterial liquid is dried in an oven at 105 ℃ for 24 hours, and then the dried iron-rich bacterial powder is obtained by grinding. Transferring the mixture of the iron-rich bacterial powder and KOH in a mass ratio of 1(ii) a Washing the obtained biological carbon material with 0.6M hydrochloric acid and deionized water respectively for three times, removing alkali and chloride ion residues, and drying in a 65 ℃ oven to obtain the biological carbon material named as Fe-BC Ferritin 。
Comparative example 1
Preparing a liquid medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) using distilled water, subpackaging 500mL in 1000mL Erlenmeyer flasks, and autoclaving at 121 ℃ for 20min; preparing 0.5M of ammonium ferrous sulfate mother liquor, and removing bacteria through a 0.22-micron filter membrane; the engineering strain pYYDT-ferritin is inoculated into a liquid culture medium in an ultra-clean bench, the culture medium is placed in a constant-temperature shaking table and cultured under the conditions of 220rpm and 30 ℃, when the concentration of the bacterial liquid reaches OD600=0.424, 2.5mL of 1M arabinose mother liquor is added, no ammonium ferrous sulfate solution is added, after 24h of culture, the bacterial liquid is collected by centrifugation at 8000rpm for 5min, and is dried for 24h in a 105 ℃ oven after being washed once by 2 mM, PH =6.8 Tris-HCl and deionized water respectively, and then the dried bacterial powder is obtained by grinding. Transferring the mixed mass ratio of the bacterial powder and KOH of 1; washing the obtained biological carbon material with 0.6M hydrochloric acid and deionized water respectively for three times, removing alkali and chloride ion residues, and drying in a 65 ℃ oven to obtain the biological carbon material named as BC Ferritin 。
Comparative example 2
Preparing liquid culture medium 2 XYT with distilled water, subpackaging 500mL in 1000mL conical flask, and high-pressure steam sterilizing at 121 deg.C for 20min; preparing 0.5M of ammonium ferrous sulfate mother liquor, and removing bacteria through a 0.22-micron filter membrane; inoculating a wild strain MR-1/WT into a liquid culture medium in a super clean bench, placing the culture medium in a constant temperature shaking table, culturing at 220rpm and 30 ℃ until the concentration of the bacterial liquid reaches OD600=0.503, adding 2.5mL of 1M arabinose mother liquor, culturing for 30 minutes, adding 2.0mL of ammonium ferrous sulfate mother liquor, culturing for 24 hours, centrifuging at 8000rpm for 5min, and collecting the bacterial liquidAfter washing with 2 mM Tris-HCl having a pH of =6.8 and deionized water once each, the resultant was oven-dried at 105 ℃ for 24 hours, and then ground to obtain a dry bacterial powder. Transferring the mixed mass ratio of the bacterial powder and KOH of 1; washing the obtained biological carbon material with 0.6M hydrochloric acid and deionized water respectively for three times, removing alkali and chloride ion residues, and drying in a 65 ℃ oven to obtain the biological carbon material named as Fe-BC WT 。
Comparative example 3
Preparing liquid culture medium 2 XYT with distilled water, subpackaging 500mL in 1000mL conical flask, and sterilizing with high pressure steam at 121 deg.C for 20min; preparing 0.5M of ammonium ferrous sulfate mother liquor, and removing bacteria through a 0.22-micron filter membrane; the preparation method comprises the steps of inoculating a wild type strain MR-1/WT into a liquid culture medium in a super 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 bacteria liquid reaches OD600=0.421, not adding ammonium ferrous sulfate mother liquor, after culturing for 24 hours, centrifuging at 8000rpm for 5min to collect the bacteria liquid, washing with 2 mM, PH =6.8 Tris-HCl and deionized water once respectively, drying in an oven at 105 ℃ for 24 hours, and grinding to obtain dry bacteria powder. Transferring the mixed bacterial powder and KOH with the mass ratio of 1; washing the obtained biological carbon material with 0.6M hydrochloric acid and deionized water respectively for three times, removing alkali and chloride ion residues, and drying in a 65 ℃ oven to obtain the biological carbon material named as BC WT 。
The biochar materials obtained in example 1 and comparative example 1 were analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in fig. 1.
In order to investigate the catalytic performance of the iron-nitrogen co-doped carbon biological carbon 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 potassium peroxymonosulfate complex salt oxidant. The concentration of bisphenol A in the solution was periodically sampled and detected at room temperature and at a rotation speed of 400rpm, and the degradation kinetic profile of the biochar material to bisphenol A is shown in FIG. 2. According to the determination result, bisphenol A in the system can be completely removed within 10 min.
30mL of 10mg/L bisphenol A solution is prepared, the pH value is adjusted to 4.0-10.0 by HCl and NaOH, 6mg of Fe-BC sample and 3mg of potassium peroxymonosulfate composite 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 400rpm of rotation speed, and the degradation kinetic curve graph of the biochar material to 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 potassium peroxymonosulfate complex salt oxidant. And (3) sampling at room temperature and at the rotation speed of 400rpm at regular time to detect the concentration of the bisphenol A in the solution, filtering distilled water after 30min to wash the Fe-BC sample, and repeating the operation to obtain the degradation kinetic curve graph of the repeatedly activated potassium monopersulfate composite salt of the biological carbon material on the bisphenol A, wherein the degradation kinetic curve graph is shown in figure 4.
Influence of adding amount of biological carbon material on 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 Fe-BC were added Ferritin And adding 0.1g/L potassium hydrogen peroxymonosulfate composite salt oxidant into the sample. The bisphenol A concentration in the solution was periodically sampled and detected at room temperature and 400rpm, and the degradation kinetics curve of bisphenol A at different dosages of the biochar material is shown in FIG. 5.
As can be seen from FIG. 5, the removal rate was gradually increased from 30% to 100% when the amount of the added biochar material was gradually increased from 0.02g/L to 0.3 g/L. When the adding amount of the biological carbon material is increased, the adsorption area and the active sites can be increased, and the bisphenol A removal efficiency can be obviously improved.
Influence of adding amount of potassium monopersulfate 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 And adding 0.2g/L, 0.1g/L, 0.05g/L and 0.02g/L potassium peroxymonosulfate composite salt oxidant into the sample respectively. The concentration of bisphenol A in the solution was periodically sampled and measured at room temperature and 400rpm, and the degradation kinetics curves of bisphenol A at different dosages of potassium monopersulfate complex salt oxidant are shown in FIG. 6.
As can be seen from FIG. 6, the removal rate of bisphenol A is significantly improved with the increase of the addition amount of the potassium monopersulfate complex salt oxidant, and when the addition amount is 0.1g/L, the removal rate of the bisphenol A solution with the concentration of 10mg/L can reach 100%, so that a more ideal removal effect is achieved.
Example 2
Preparing liquid medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, subpackaging 500mL in 1000mL conical flasks, and autoclaving at 121 ℃ for 20min; preparing 0.5M of ammonium ferrous sulfate mother liquor, and removing bacteria through a 0.22-micron filter membrane; the engineering strain pYYDT-ferritin is inoculated into a liquid culture medium in a super clean bench, the culture medium is placed in a constant temperature shaking table and is cultured under the conditions of 220rpm and 30 ℃, when the concentration of bacterial liquid reaches OD600=0.432, 2.5mL of 1M arabinose mother liquor is added for culturing for 30 minutes, 2.0mL of ammonium ferrous sulfate mother liquor is added, after 24 hours of culture, the bacterial liquid is collected by centrifugation at 8000rpm for 5 minutes, tris-HCl with the concentration of 20mM and PH =6.8 and deionized water are respectively washed once and then dried in an oven at the temperature of 105 ℃ for 24 hours, and then, the dried iron-rich bacterial powder is obtained by grinding. Transferring the mixed mass ratio of the iron-rich bacterial powder and KOH (potassium hydroxide) to a corundum crucible of 1.5, placing the corundum crucible in a tubular furnace, introducing inert gas nitrogen into the tubular furnace at room temperature, wherein the gas flow rate is 20mL/min, calcining the mixture under the nitrogen atmosphere, the heating rate is 5 ℃/min, the calcining temperature is 400 ℃, the calcining time is 4 hours, and naturally cooling the mixture to room temperature to obtain a solid biological carbon material; the obtained biocarbon material was washed three times with 0.6M hydrochloric acid and deionized water, respectively, to remove alkali and chloride ion residues, and dried in an oven at 65 ℃ to obtain a biocarbon material, and in order to examine the catalytic performance of the iron-nitrogen co-doped carbon biocarbon material prepared in this example 2, the experiment was as follows: 30mL of 10mg/L bisphenol A solution was prepared, and 6mg of the sample of example 2 and 3mg of potassium monopersulfate complex salt as an oxidizing agent were added. The degradation kinetic curve of the biochar material to bisphenol A is shown in FIG. 7 by sampling and detecting the concentration of bisphenol A in the solution at room temperature and at 400rpm. According to the determination result, the bisphenol A in the system can be effectively removed within 30min, and the removal rate reaches 90% within 30 min.
Example 3
Preparing liquid medium 2 XYT (Tryptone: 16g/L Yeast Extract:10g/LNaCl:5 g/L) with distilled water, subpackaging 500mL in 1000mL conical flasks, and autoclaving at 121 ℃ for 20min; preparing 0.5M ferrous glycinate mother liquor, and removing bacteria through a 0.22-micron filter membrane; the engineering strain pYYDT-fertilitin is inoculated into a liquid culture medium in a super clean bench, the culture medium is placed in a constant temperature shaking table and cultured under the conditions of 220rpm and 30 ℃, when the bacterial liquid concentration reaches OD600=0.432, 2.5mL of 1M arabinose mother liquor is added for culturing for 30 minutes, 2.0mL of ferrous glycinate mother liquor is added, after 24 hours of culture, the centrifugal operation is carried out at 8000rpm for 5 minutes to collect the bacterial liquid, tris-HCl with the concentration of 20mM and PH =6.8 and deionized water are respectively used for cleaning once, then drying is carried out in an oven at the temperature of 105 ℃ for 24 hours, and then grinding is carried out to obtain dry iron-rich bacterial powder. Transferring the mixed mass ratio of the iron-rich bacterial powder and KOH (potassium hydroxide) to a corundum crucible which is 1; the obtained biocarbon material was washed three times with 0.6M hydrochloric acid and deionized water, respectively, to remove alkali and chloride ion residues, and dried in an oven at 65 ℃ to obtain a biocarbon material, and in order to examine the catalytic performance of the iron-nitrogen co-doped carbon biocarbon material prepared in this example 3, the experiment was as follows: 30mL of 10mg/L bisphenol A solution was prepared, and 6mg of the sample of example 2 and 3mg of potassium monopersulfate complex salt as an oxidizing agent were added. The degradation kinetic curve of the biochar material to bisphenol A is shown in FIG. 8, which is obtained by sampling and detecting the concentration of bisphenol A in the solution at room temperature and 400rpm. According to the determination result, the bisphenol A in the system can be effectively removed within 30min, and the removal rate reaches 99% within 30 min.
Claims (10)
1. A preparation method of an iron-nitrogen co-doped biological carbon material based on microbial enrichment is characterized by comprising the following steps:
s1) culturing Shewanella engineering bacteria carrying ferritin ferriritin coding genes, inducing ferritin expression, adding ferrous salt containing nitrogen elements, and continuing culturing to obtain iron-rich bacteria;
s2) mixing the iron-rich bacteria with alkaline substances, and calcining in a protective atmosphere to obtain the microorganism enrichment-based iron-nitrogen co-doped biological carbon material.
2. The process according to claim 1, wherein the Shewanella engineered bacterium harboring a gene encoding ferritin ferriritin is prepared by the following method:
and (3) transforming the plasmid pYYDT-ferritin into Shewanella to obtain the Shewanella engineering bacteria carrying ferritin-ferritin coding genes.
3. The method according to claim 2, wherein the Shewanella is MR-1 Shewanella.
4. The process according to claim 1, wherein the culture medium used for culturing the Shewanella engineered bacteria carrying the ferritin ferricin-encoding gene in the step S1) is 2 XYT medium;
using arabinose as an inducer to induce ferritin expression;
the ferrous salt containing nitrogen element is ammonium ferrous sulfate and/or ferrous glycinate.
5. The method according to claim 1, wherein the step S1) of culturing the Shewanella engineered bacteria carrying the ferritin ferriritin-encoding gene has an OD600 of 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 ferritin expression is 20-50 min;
the addition amount of the ferrous salt containing nitrogen elements ensures that the concentration of the 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 basic substance is selected from the group consisting of alkali metal hydroxides; the mass ratio of the iron-rich bacteria to the alkaline substances is 1: (0.5-1.5).
7. The method according to claim 1, wherein the calcination is carried out at a temperature of 300 ℃ to 600 ℃; the calcining time is 1-4 h; the temperature rise rate of the calcination is 3-8 ℃/min.
8. 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.
9. The use of the iron-nitrogen co-doped biocarbon material based on microbial enrichment prepared by the preparation method of any one of claims 1 to 7 as a persulfate activator.
10. A method for degrading organic pollutants in a water body is characterized by comprising the following steps:
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, is used as a catalyst, persulfate is used as an oxidant, and water containing organic pollutants is treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211510117.5A CN115739023B (en) | 2022-11-29 | 2022-11-29 | Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211510117.5A CN115739023B (en) | 2022-11-29 | 2022-11-29 | Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115739023A true CN115739023A (en) | 2023-03-07 |
| CN115739023B CN115739023B (en) | 2024-02-09 |
Family
ID=85340088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211510117.5A Active CN115739023B (en) | 2022-11-29 | 2022-11-29 | Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739023B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967261A (en) * | 2016-05-26 | 2016-09-28 | 许婷 | Sewage treatment agent special for printing and dyeing wastewater and preparation method of sewage treatment agent |
| CN106252672A (en) * | 2016-08-19 | 2016-12-21 | 华南理工大学 | A kind of method utilizing microorganism and iron mine preparation doping carbon catalysis material |
| CN108754658A (en) * | 2018-06-25 | 2018-11-06 | 中国科学技术大学 | A kind of preparation method of bacteria cellulose composite material yarn |
| CN109604624A (en) * | 2019-01-08 | 2019-04-12 | 哈尔滨工业大学 | A kind of method and application preparing nano zero valence iron using water treatment plant's iron containing sludge |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
| CN110694636A (en) * | 2019-10-08 | 2020-01-17 | 中南大学 | Carbon-based-multi-metal composite nano catalytic material and preparation method and application thereof |
| CN111717914A (en) * | 2019-03-20 | 2020-09-29 | 四川大学 | Method for preparing magnetic biological carbon material by converting iron-rich microorganisms |
-
2022
- 2022-11-29 CN CN202211510117.5A patent/CN115739023B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967261A (en) * | 2016-05-26 | 2016-09-28 | 许婷 | Sewage treatment agent special for printing and dyeing wastewater and preparation method of sewage treatment agent |
| CN106252672A (en) * | 2016-08-19 | 2016-12-21 | 华南理工大学 | A kind of method utilizing microorganism and iron mine preparation doping carbon catalysis material |
| CN108754658A (en) * | 2018-06-25 | 2018-11-06 | 中国科学技术大学 | A kind of preparation method of bacteria cellulose composite material yarn |
| CN109604624A (en) * | 2019-01-08 | 2019-04-12 | 哈尔滨工业大学 | A kind of method and application preparing nano zero valence iron using water treatment plant's iron containing sludge |
| CN111717914A (en) * | 2019-03-20 | 2020-09-29 | 四川大学 | Method for preparing magnetic biological carbon material by converting iron-rich microorganisms |
| CN110227534A (en) * | 2019-07-16 | 2019-09-13 | 河南省科学院化学研究所有限公司 | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge |
| CN110694636A (en) * | 2019-10-08 | 2020-01-17 | 中南大学 | Carbon-based-multi-metal composite nano catalytic material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUN CHEN 等: ""Activating peroxymonosulfate using carbon from cyanobacteria as support for zero‑valent iron"", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH》, vol. 29, pages 73353 * |
| 李娇娇: ""生物炭负载零价铁活化过硫酸盐降解阿特拉津的机制及其对土壤环境的影响"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 04, pages 027 - 419 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115739023B (en) | 2024-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111054421A (en) | Graphite-like carbon nitride doped modified microsphere catalyst and preparation method and application thereof | |
| CN110665512B (en) | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof | |
| CN113061441B (en) | Biochar loaded iron material for oxidizing and repairing organic pollution of soil water body and preparation method and application thereof | |
| CN112441659B (en) | Method for degrading and treating organic pollutants by activating persulfate through multi-stage mesoporous biochar material | |
| CN109876810B (en) | Preparation method and application of magnetic microalgae-based biochar | |
| CN113209970B (en) | Preparation method and application of carbon-based catalyst prepared from excess sludge | |
| CN108970608B (en) | Supported noble metal catalyst with coating structure, preparation method thereof and application thereof in Cu (II) liquid-phase catalytic reduction | |
| CN110841654B (en) | Zero-valent iron-loaded iron-manganese oxide composite material, and preparation method and application thereof | |
| CN114057279A (en) | Method for accelerating iron circulation by using hydrothermal carbon to promote catalytic degradation of organic pollutants | |
| CN111774045A (en) | Regeneration method of diatomite adsorbent | |
| CN113083369A (en) | electro-Fenton catalyst derived based on iron-based metal organic framework and preparation method and application thereof | |
| CN115155537A (en) | FeOOH functionalized acrylic fiber and preparation method and application thereof | |
| CN112374583B (en) | Preparation and application of functionalized sludge-based carbon three-dimensional particle electrode | |
| CN112121798B (en) | Method for degrading chloramphenicol in water under catalysis of MIL-101 (Fe/Co) derived magnetic cobalt ferrite and application thereof | |
| CN117645356A (en) | Method for controlling disinfection byproducts in drinking water by ozone catalytic oxidation | |
| CN115739023A (en) | Iron-nitrogen co-doped biological carbon material based on microbial enrichment, and preparation method and application thereof | |
| CN115382551B (en) | Three-dimensional carbonaceous functional cathode material based on potassium ferrate modification, and preparation method and application thereof | |
| CN115634691B (en) | Preparation method and application of hollow nano catalyst for decomposing phenolic organic pollutants | |
| CN112758922B (en) | Preparation process and system of high-pyridine nitrogen-doped activated carbon | |
| CN111974408B (en) | Immobilized heterogeneous Fenton catalyst and preparation method and application thereof | |
| CN114377696A (en) | Biomembrane-based BiOClxBr(1-x)/Au/MnO2Composite material and preparation method and application thereof | |
| CN113578365A (en) | Preparation method and application of surface-modified nano-iron-manganese composite catalyst | |
| CN106669678B (en) | Preparation method of catalyst for electrocatalytic degradation of organic wastewater | |
| CN115739162B (en) | Copper-iron bimetal composite carbon nitride Fenton catalyst and preparation method and application thereof | |
| CN116688988A (en) | Cu monoatomic jack hexagonal phase WO 3 Catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |