CN113502304A - FeS nano composite material, preparation method and application thereof - Google Patents

FeS nano composite material, preparation method and application thereof Download PDF

Info

Publication number
CN113502304A
CN113502304A CN202110806646.9A CN202110806646A CN113502304A CN 113502304 A CN113502304 A CN 113502304A CN 202110806646 A CN202110806646 A CN 202110806646A CN 113502304 A CN113502304 A CN 113502304A
Authority
CN
China
Prior art keywords
fes
nano
bacteria
water
culture
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.)
Pending
Application number
CN202110806646.9A
Other languages
Chinese (zh)
Inventor
李文卫
付贤钟
柳后起
朱勇坤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202110806646.9A priority Critical patent/CN113502304A/en
Publication of CN113502304A publication Critical patent/CN113502304A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P9/00—Preparation of organic compounds containing a metal or atom other than H, N, C, O, S or halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

The invention provides a preparation method of a FeS nano composite material. Compared with the prior art, the invention utilizes dissimilatory metal reducing bacteria, takes organic matters as metabolic substrates, takes water-soluble sulfur-containing compounds and ferric iron salt as electron acceptors after generating electrons, and produces Fe through biological reduction2+And S2‑FeS nano particles are formed by combination, the FeS nano particles anchored on the cell surface are coupled with bacteria to form a bacteria-nano material heterozygote, and the toxic action of heavy metal ions on bacterial cells is relieved while heavy metals are effectively removed by a large amount of FeS nano particles gathered outside cells; sodium (A)The good conductivity of the nano FeS further enhances the extracellular electron transfer capability of the bacteria, enhances the extracellular reduction of the bacteria to heavy metals and the regeneration of the FeS, simultaneously provides an electron acceptor for the bacteria to synthesize the nano FeS again after the nano FeS reacts with the heavy metals, and can realize the cyclic regeneration of the nano FeS.

Description

FeS nano composite material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a FeS nano composite material, and a preparation method and application thereof.
Background
A large amount of wastewater rich in heavy metals is generated in the production and processing processes of various industries such as mining, metallurgy, electroplating, electronic manufacturing and the like, wherein the common heavy metals such as chromium, copper, nickel, zinc, lead and the like have strong biotoxicity and are seriously dangerous for ecological environment safety and human health. At present, the common methods for treating heavy metal wastewater comprise adsorption, flocculation, membrane treatment, ion exchange, chemical precipitation and the like. Although effective, the physical and chemical methods have the defects of high cost, low removal efficiency and the like, and the generated sludge, concentrated solution, toxic gas and the like containing a large amount of heavy metals have secondary environmental pollution risks. In particular, the commonly adopted sulfide precipitation method usually needs to add sodium sulfide or calcium sulfide as a reducing agent and a precipitating agent, so that heavy metal sludge and residual S in effluent water are generated2-And generation of H2S gas can also cause corrosion to equipment. In future, if the heavy metal sludge is brought into hazardous waste management, the treatment method is severely limited.
In response to the problems of the conventional sulfide precipitation method, researchers have proposed a new technology of using ferrous sulfide (FeS) nano material instead of sodium sulfide/calcium sulfide in recent years. Since FeS is insoluble in water, S does not exist in effluent2-Secondary pollution, and can efficiently remove various heavy metals through various mechanisms such as reduction, ion exchange, adsorption and the like. However, FeS nanoparticles tend to agglomerate and are easily oxidized to iron oxides in the presence of air and trace amounts of moisture, thereby reducing their reactivity. Thus, it is often necessary to load the carrier material and to strictly control the storage and transportation conditions, thereby limiting its practical application.
Compared with a physical and chemical method, the biological method has huge potential advantages and development prospects in the aspect of heavy metal wastewater treatment. The biological method mainly utilizes the adsorption and reduction of microorganisms to remove various heavy metals, and has the advantages of low cost, simple operation, small sludge production and environmental friendliness. For example, dissimilatory metal-reducing bacteria can directly reduce various toxic high-valence heavy metal ions such as Cr (VI) and Cu (II) into non-toxic low-valence ions or metal simple substances, and sulfate-reducing bacteria can utilize hydrogen sulfide generated by the metabolism of the sulfate-reducing bacteria to combine with the heavy metal ions to form metal sulfide precipitates, so that the metal sulfide precipitates can be removed from water. However, the heavy metal wastewater has complex components and strong biological toxicity, and the activity of microorganisms is often severely inhibited when the concentration of heavy metal ions is high, so that the treatment efficiency is low, and the practical engineering application of the method is limited.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a FeS nanocomposite, a preparation method thereof and an application thereof, wherein the FeS nanocomposite can realize efficient removal of heavy metals by coupling chemical and biological processes.
The invention provides a preparation method of a FeS nano composite material, which is characterized by comprising the following steps:
s) under the anaerobic condition, carrying out shake culture on dissimilatory metal reducing bacteria in a culture solution containing water-soluble ferric salt and water-soluble sulfur-containing compounds to obtain the FeS nano composite material.
Preferably, the dissimilatory metal-reducing bacteria are selected from one or more of Shewanella onandra, Thiodermabacter and Aeromonas hydrophila.
Preferably, the water-soluble ferric salt is selected from one or more of ferric chloride, ferric sulfate, ferric ammonium sulfate and ferric citrate; the water-soluble sulfur-containing compound is selected from one or more of thiosulfate, sulfite and sulfide.
Preferably, the step S) is specifically:
dispersing dissimilatory metal reducing bacteria in the culture solution after the deoxidization and sterilization treatment to obtain a bacterial solution;
under the anaerobic condition, adding water-soluble ferric salt and water-soluble sulfur-containing compounds into the bacterial liquid to obtain a culture system, and performing shaking culture to obtain the FeS nano composite material.
Preferably, OD of the bacterial liquid6000.1 to 3.
Preferably, the concentration of the aqueous solution ferric salt in the culture system is 0.1-10 mmol/L; the concentration of the water-soluble sulfur-containing compound in the culture system is 0.1-10 mmol/L.
Preferably, the temperature of the shaking culture is 4-50 ℃; the rotation speed of the shaking culture is 50-250 rpm; the shaking culture time is 5-24 h.
The invention also provides the FeS nano composite material prepared by the preparation method, which comprises dissimilatory metal reducing bacteria; FeS nano materials are distributed on the cell surface and in the cell membrane of the dissimilatory metal reducing bacteria.
The invention also provides application of the FeS nano composite material prepared by the preparation method in treatment of heavy metal-containing wastewater.
Preferably, the heavy metal-containing wastewater comprises hexavalent chromium ions.
The invention provides a preparation method of a FeS nano composite material, which comprises the following steps: s) under the anaerobic condition, carrying out shake culture on dissimilatory metal reducing bacteria in a culture solution containing water-soluble ferric salt and water-soluble sulfur-containing compounds to obtain the FeS nano composite material. Compared with the prior art, the invention utilizes dissimilatory metal reducing bacteria, takes organic matters as metabolic substrates, takes water-soluble sulfur-containing compounds and ferric iron salt as electron acceptors after generating electrons, and produces Fe through biological reduction2+And S2-FeS nano particles are formed by combination, and the FeS nano particles anchored on the cell surface are coupled with bacteria to form a bacteria-nano material heterozygote, so that the FeS nano particles are uniformly dispersed, the oxidation of the FeS nano particles in the extraction and purification processes can be effectively avoided, and the catalytic activity of the FeS nano particles is improved; and a large amount of FeS nano-particles gathered outside cells effectively remove heavy metals and simultaneously relieve the toxic action of heavy metal ions on bacterial cells; moreover, the nano FeS uniformly distributed on the intracellular, periplasm and cell membrane causes good conductivity, so that the extracellular electron transfer capability of the bacteria is further enhanced, the extracellular reduction of the bacteria on heavy metals and the regeneration of the FeS are enhanced, meanwhile, the products obtained after the reaction of the nano FeS and the heavy metals are mainly ferric iron, elemental sulfur and polysulfide ions, an electron acceptor is provided for the bacteria to synthesize the nano FeS again, and the cyclic regeneration of the nano FeS can be realized.
Drawings
FIG. 1 is an SEM image of a bacteria-material hybrid in the course of biosynthesis of nanoparticles in example 1 of the present invention;
FIG. 2 is a HAADF-TEM image and an EDX image of a section of a bacterium-nanomaterial hybrid during biosynthesis of nanoparticles in example 1 of the present invention;
FIG. 3 is an XRD pattern of the bacteria-nanomaterial hybrid during biosynthesis of nanoparticles in example 1 of the present invention;
FIG. 4 is a graph of experimental kinetic data of reduction of methyl orange by bacteria-nano FeS hybrid in situ in example 1 of the present invention;
FIG. 5 is a graph showing the experimental kinetic data of hexavalent chromium reduction in situ using a bacteria-nano FeS hybrid in example 1 of the present invention;
FIG. 6 is a graph showing experimental kinetic data of heavy metals in the actual electroplating wastewater treated in situ with the bacteria-nano FeS hybrid in example 2 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 a FeS nano composite material, which comprises the following steps: s) under the anaerobic condition, carrying out shake culture on dissimilatory metal reducing bacteria in a culture solution containing water-soluble ferric salt and water-soluble sulfur-containing compounds to obtain the FeS nano composite material.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The invention mainly utilizes dissimilatory metal reducing bacteria, takes organic matters as metabolic substrates, generates electrons, takes water-soluble sulfate and ferric iron salt as electron acceptors, and produces Fe through biological reduction2+And S2-And combining to form FeS nano particles, thereby obtaining the FeS nano composite material. The dissimilatory metal-reducing bacteria include, but are not limited to, Shewanella oneiden (Shewanella oneiden)sis), one or more of Bacillus subtilis and Aeromonas hydrophila (Aeromonas hydrophila); in the embodiment provided by the invention, the dissimilatory metal reducing bacterium is Shewanella oneidensis MR-1, and compared with other strains, Shewanella oneidensis has the advantages of high growth speed, mature culture process, clear genetic background, extracellular electron transfer capacity (continuous reducing power) and the like.
In the invention, the dissimilatory metal reducing bacteria are preferably obtained by culturing dissimilatory metal reducing bacteria; the culture method is well known to those skilled in the art, and is not particularly limited, and when the shewanella onanthraceae is taken as an example, the shewanella onanthraceae strain is inoculated into an LB liquid medium for constant temperature shaking culture to obtain a suspension; then, the suspension was mixed with an LB liquid medium in a volume ratio of 1: (50-150) mixing and then continuously activating to obtain Shewanella onadatuma; the temperature of the shaking culture is preferably 4-50 ℃, more preferably 10-40 ℃, further preferably 20-35 ℃ and most preferably 30 ℃; the rotation speed of the shaking culture is preferably 50-250 rpm, more preferably 100-250 rpm, and further preferably 150-200 rpm; the shaking culture time is preferably 5-20 h, more preferably 10-14 h, and further preferably 12 h; the volume ratio of the suspension to the LB liquid medium is preferably 1: (80-120), more preferably 1:100, respectively; the activation is preferably carried out under the same shaking culture conditions; the activation time is preferably 10-24 hours, more preferably 14-20 hours, and still more preferably 16-18 hours.
Carrying out shake culture on dissimilatory metal reducing bacteria in a culture solution containing water-soluble ferric salt and aqueous solution sulfur-containing compounds; wherein, the water-soluble ferric salt is preferably one or more of ferric chloride, ferric sulfate, ferric ammonium sulfate and ferric citrate; the concentration of the water-soluble ferric salt in the culture solution containing the water-soluble ferric salt and the water-soluble sulfur-containing compound is preferably 0.1-10 mmol/L, more preferably 0.1-7 mmol/L, still more preferably 0.1-5 mmol/L, still more preferably 0.1-3 mmol/L, still more preferably 0.1-1 mmol/L, and most preferably 0.2-0.5 mmol/L; the water-soluble sulfur-containing compound is preferably one or more of thiosulfate, sulfite and sulfide; the cations in the thiosulfate, sulfite and sulfide salts are preferably sodium ions and/or potassium ions; the concentration of the water-soluble sulfur-containing compound in the culture solution containing the water-soluble ferric salt and the water-soluble sulfur-containing compound is preferably 0.1-10 mmol/L, more preferably 0.1-7 mmol/L, still more preferably 0.1-5 mmol/L, still more preferably 0.1-3 mmol/L, still more preferably 0.1-1 mmol/L, and most preferably 0.2-0.5 mmol/L; the temperature of the shaking culture is preferably 4-50 ℃, more preferably 10-40 ℃, further preferably 20-35 ℃ and most preferably 30 ℃; the rotation speed of the shaking culture is preferably 50-250 rpm, more preferably 100-250 rpm, and further preferably 150-200 rpm; the time of shaking culture is preferably 5-24 h, and more preferably 10-24 h.
In the present invention, the above steps are more preferably and specifically: dispersing dissimilatory metal reducing bacteria in the culture solution after the deoxidization and sterilization treatment to obtain a bacterial solution; under the anaerobic condition, adding water-soluble ferric salt and water-soluble sulfur-containing compounds into the bacterial liquid to obtain a culture system, and performing shaking culture to obtain the FeS nano composite material.
The culture solution is preferably a mineral salt culture solution; the mineral salt medium solution preferably comprises 0.2-0.6 g/L of sodium chloride, 0.1-0.4 g/L of ammonium sulfate, 0.1-0.4 g/L of potassium dihydrogen phosphate, 0.1-0.4 g/L of dipotassium hydrogen phosphate, 0.05-0.2 g/L of magnesium sulfate and 10-40 mM of sodium lactate, more preferably comprises 0.3-0.5 g/L of sodium chloride, 0.15-0.3 g/L of ammonium sulfate, 0.15-0.3 g/L of potassium dihydrogen phosphate, 0.15-0.3 g/L of dipotassium hydrogen phosphate, 0.05-0.15 g/L of magnesium sulfate and 15-30 mM of sodium lactate, further preferably comprises 0.4-0.5 g/L of sodium chloride, 0.2-0.25 g/L of ammonium sulfate, 0.2-0.25 g/L of potassium dihydrogen phosphate, 0.2-0.25 g/L of dipotassium hydrogen phosphate, 0.2-0.25 g/L of magnesium sulfate and 0.12-0.25 g/L of sodium lactate, most preferably comprises 0.46-0.25 g/L of sodium chloride, and 0.5-0.4-0.5 mM of sodium sulfate, 0.225g/L potassium dihydrogen phosphate, 0.225g/L dipotassium hydrogen phosphate, 0.05-0.06 g/L magnesium sulfate and 20mM sodium lactate; the pH value of the culture solution is preferably 7-7.5; the culture fluid is preferably deoxygenated by nitrogen aeration; the time for nitrogen exposure is preferably 20-30 min; the sterilization conditions are preferably 121 ℃ and 20 min.
Reducing dissimilatory metalDispersing in the culture solution after the deoxidization and sterilization treatment to obtain a bacterial solution; OD of the bacterial liquid600I.e., OD of dissimilatory metal-reducing bacteria in the culture broth600Preferably 0.1 to 3, more preferably 0.3 to 2, still more preferably 0.3 to 1.5, and most preferably 0.5 to 1.
Under the anaerobic condition, adding water-soluble ferric salt and water-soluble sulfur-containing compounds into the bacterial liquid to obtain a culture system, and performing shaking culture to obtain the FeS nano composite material. The concentration of the aqueous trivalent ferric salt in the culture system is preferably 0.1-10 mmol/L, more preferably 0.1-7 mmol/L, still more preferably 0.1-5 mmol/L, still more preferably 0.1-3 mmol/L, still more preferably 0.1-1 mmol/L, and most preferably 0.2-0.5 mmol/L; the concentration of the water-soluble sulfur-containing compound in the culture system is preferably 0.1-10 mmol/L, more preferably 0.1-7 mmol/L, still more preferably 0.1-5 mmol/L, still more preferably 0.1-3 mmol/L, still more preferably 0.1-1 mmol/L, and most preferably 0.2-0.5 mmol/L; the temperature of the shaking culture is preferably 4-50 ℃, more preferably 10-40 ℃, further preferably 20-35 ℃ and most preferably 30 ℃; the rotation speed of the shaking culture is preferably 50-250 rpm, more preferably 100-250 rpm, and further preferably 150-200 rpm; the time of shaking culture is preferably 5-24 h, and more preferably 10-24 h.
After the shaking culture, the culture solution containing the FeS nano composite material can be directly used without any treatment, such as heavy metal wastewater treatment, or the FeS nano composite material can be obtained after simple centrifugation; the oxidation process of the nano FeS in the extraction and purification processes can be effectively avoided, the catalytic activity of the biosynthetic nano FeS is ensured, and the operation cost is reduced.
The invention utilizes dissimilatory metal reducing bacteria to take organic matters as metabolic substrates, generates electrons, takes water-soluble sulfur-containing compounds and ferric iron salt as electron acceptors, and produces Fe through biological reduction2+And S2-FeS nano particles are formed by combination, and the FeS nano particles anchored on the cell surface are coupled with bacteria to form a bacteria-nano material heterozygote, so that the FeS nano particles are uniformly dispersed, the oxidation of the FeS nano particles in the extraction and purification processes can be effectively avoided, and the catalytic activity of the FeS nano particles is improved; and are accumulated in a large amount in cellsThe external FeS nano-particles effectively remove heavy metals and simultaneously relieve the toxic action of heavy metal ions on bacterial cells; moreover, the nano FeS uniformly distributed on the intracellular, periplasm and cell membrane causes good conductivity, so that the extracellular electron transfer capability of the bacteria is further enhanced, the extracellular reduction of the bacteria on heavy metals and the regeneration of the FeS are enhanced, meanwhile, the products obtained after the reaction of the nano FeS and the heavy metals are mainly ferric iron, elemental sulfur and polysulfide ions, an electron acceptor is provided for the bacteria to synthesize the nano FeS again, and the cyclic regeneration of the nano FeS can be realized.
The invention also provides the FeS nano composite material prepared by the method, which comprises dissimilatory metal reducing bacteria; FeS nano materials are distributed on the cell surface and in the cell membrane of the dissimilatory metal reducing bacteria.
The invention also provides application of the FeS nano composite material prepared by the method in treatment of heavy metal-containing wastewater.
According to the invention, the microbial synthesized nano FeS and cells form a composite system together, complementary and synergistic advantages of the nano FeS and the cells are exerted, and the synergistic effect of the biological synthesized nano FeS and the microorganisms is utilized in situ, so that economic, efficient and sustainable treatment of the heavy metal wastewater is realized.
The heavy metal-containing wastewater preferably comprises one or more of hexavalent chromium ions, copper ions and zinc ions; the concentration of hexavalent chromium ions in the heavy metal-containing wastewater is preferably 10-100 mg/L; in the embodiment provided by the invention, the concentration of hexavalent chromium ions in the heavy metal-containing wastewater is specifically 50 mg/L.
According to the invention, the method for treating the wastewater containing the heavy metals comprises the following steps: mixing the heavy metal-containing wastewater with the culture solution containing the FeS nano composite material obtained after the shaking culture for the shaking culture; the temperature of the shaking culture is preferably 4-50 ℃, more preferably 10-40 ℃, further preferably 20-35 ℃ and most preferably 30 ℃; the rotation speed of the shaking culture is preferably 50-250 rpm, more preferably 100-250 rpm, and further preferably 150-200 rpm; after the treatment of the solution returning to black is finished, the wastewater containing heavy metals can be added again for recycling.
The FeS nano composite material prepared by the invention fully utilizes the strong reducibility and conductivity of the nano FeS synthesized by the biology and the protection effect of the nano FeS on bacterial cells. By comparing the extracellular electron transfer capacity of Shewanella under the condition of the existence of nano FeS synthesis, the biosynthetic nano FeS can accelerate the extracellular electron transfer of dissimilatory metal reduction bacteria, so that the in-situ regeneration of FeS is promoted and the removal efficiency of heavy metals is improved. Meanwhile, a large amount of nano FeS secreted to the outside of the cell can efficiently reduce heavy metal, effectively protect bacterial cells from the toxic action of heavy metal ions, improve the heavy metal tolerance of the bacteria and maintain a high activity metabolism level. Moreover, the invention realizes the high-efficiency removal of heavy metals and the biological cycle regeneration of the nano FeS. After the nano FeS and the heavy metal are subjected to redox reaction, products of the nano FeS mainly comprise ferric iron, elemental sulfur and polysulfide ions, and the substances can still be further used as electron acceptors by dissimilatory metal reducing bacteria to reduce and generate the nano FeS, so that the cyclic regeneration of the nano material after the heavy metal is removed is realized. The high efficiency, stability and sustainability of the invention embody enormous performance advantages and practical application potential.
In order to further illustrate the present invention, the following examples are provided to describe a FeS nanocomposite, its preparation method and application in detail.
The reagents used in the following examples are all commercially available.
Example 1
Typical dissimilatory metal reducing bacterium Shewanella oneidensis MR-1 is selected to carry out biosynthesis of nano FeS, and observation, characterization and performance test are carried out on the obtained nano material and a bacterium-nano material hybrid, namely the FeS nano composite material.
(1) Culture of Shewanella: selecting a strain of Shewanella oneidensis MR-1; inoculating Shewanella strain into 3mL LB liquid culture medium (containing yeast extract 5g/L, tryptone 10g/L and sodium chloride 10g/L, pH 7), and culturing at constant temperature under shaking (30 deg.C, 200rpm) for 12h to obtain bacterial liquid; transferring the bacterial liquid into 200mL of LB culture medium according to the volume ratio of 1:100, and continuously activating for 16h under the same condition to obtain bacterial liquid;
(2) preparation of anaerobic mineral salt medium system: the mineral salt culture medium comprises NaCl 0.460g/L, (NH)4)2SO4 0.225g/L,KH2PO4 0.225g/L,K2HPO4 0.225g/L,MgSO4·7H2O0.117 g/L, sodium lactate 20 mM; fully aerating and deoxidizing with high-purity nitrogen (20-30 min), sealing and sterilizing (121 ℃, 20 min);
(3) biosynthesis of nano-FeS and generation of bacteria-nanomaterial hybrid (FeS nanocomposite): centrifugally collecting the obtained bacterial liquid, washing for 2-3 times by using a sterile mineral salt culture medium, then carrying out heavy suspension, transferring the bacterial suspension into an anaerobic mineral salt culture medium system, and controlling the final bacterial density to be OD according to concentration conversion6000.5. Sequentially adding water-soluble ferric salt (FeCl) with final concentration of 0.2mM into an anaerobic system under anaerobic condition3) And 0.5mM of a water-soluble sulfur-containing compound (Na)2S2O3). Carrying out constant temperature shaking culture at 30 ℃, wherein the rotating speed is 200rpm, and the culture time is 24h, thus obtaining the biosynthetic nano FeS and the bacteria-nano material heterozygote (FeS nano composite material) coated by the biosynthetic nano FeS.
The biosynthetic nano FeS prepared in this example and its coated bacteria-nanomaterial hybrid were subjected to performance index testing:
SEM characterization sample preparation: taking a proper amount of the solution synthesized in the step (3) in an anaerobic workstation, centrifuging at 6000rpm for 5min, discarding the supernatant, washing twice with sterile ultrapure water, adding 2.5% glutaraldehyde solution for resuspension and precipitation, and fixing at 4 ℃ for more than 4 h. Dehydrating by adopting ethanol solution with gradient concentration, finally dripping 10 mu L of material dispersed in absolute ethanol on a copper sheet, placing the copper sheet in an anaerobic workstation, airing, and then carrying out scanning electron microscope characterization. FIG. 1 is an SEM image of a bacteria-material hybrid in the course of biosynthesis of nanoparticles in example 1. As shown in FIG. 1, a large amount of granular nano-materials are distributed on the surface of a single bacterial cell, wherein the particle size of the nano-particles is about 30-60 nm.
TEM characterization sample preparation: taking a proper amount of the solution synthesized in the step (3) in an anaerobic workstation, centrifuging at 6000rpm for 5min, and discarding the supernatant. The pellet was resuspended with 2.5% glutaraldehyde and 4% paraformaldehyde and fixed for 12 h. And (3) washing for 3 times by using PBS, dehydrating by using ethanol with a concentration gradient, wrapping by using epoxy resin, cutting into nanosheets with the thickness of 50-100 nm, and placing on a copper net for transmission electron microscope characterization. FIG. 2 is HAADF-TEM image and EDX image of a section of a bacterium-material hybrid during biosynthesis of nanoparticles in example 1. As shown in FIG. 2A, the synthesized nano-materials are widely distributed in cells, on membranes and outside cells. Fig. 2B is an EDX spectrum, and the elemental analysis results confirm the presence of Fe and S elements in the nanoparticles.
XRD characterization sample preparation: taking a proper amount of the solution synthesized in the step (3) in an anaerobic workstation, centrifuging at 12000rpm for 20min, discarding the supernatant, cleaning with sterile ultrapure water for 3 times, and drying in a freeze dryer. And grinding the dried black solid into uniform powder by using an agate mortar, and taking a proper amount of powder for X-ray diffraction analysis and characterization. Fig. 3 is an XRD pattern of the bacteria-material hybrid during biosynthesis of nanoparticles in example 1. Compared with a standard card (JADE6 PDF #86-0839), the characteristic peaks of the nano-material synthesized in the example 1 at the 2 theta positions of 17.6 degrees, 30.1 degrees and 49.6 degrees respectively correspond to the characteristic peaks of FeS (marunolite) at the crystal planes of (001), (101) and (200), and the phase composition of the obtained nano-material is mainly FeS (marunolite).
The above characterization results confirm the biosynthesis of nano FeS and also confirm that the bacteria are coated by FeS nanoparticles synthesized by the bacteria, and the formed FeS nanocomposite is a bacteria-material hybrid.
(4) Biosynthetic nano FeS and its coated bacteria-nanomaterial hybrids were used in situ to remove Methyl Orange (MO):
directly adding Methyl Orange (MO) with the final concentration of 100mg/L into the solution synthesized in the step (3), and measuring the residual MO content in the solution at 0.5, 1, 2, 4, 6 and 8 hours.
FIG. 4 shows the effect of the experiment of reducing methyl orange in situ with the bacteria-nano FeS hybrid in example 1. It can be seen from the figure that compared with the pure bacterial group without nano FeS, the bacterial-nano FeS hybrid can realize high-efficiency MO reduction (the reduction rate can reach 99.9% in 4 h), and the key promotion effect of the biosynthetic nano FeS in the extracellular electron transfer is directly proved. By comparing the extracellular MO reduction capacity of Shewanella under the condition of existence of nano FeS synthesis, the biosynthetic nano FeS can accelerate extracellular electron transfer of dissimilatory metal reduction bacteria, so that in-situ regeneration of FeS is promoted and the removal efficiency of heavy metals is improved.
(5) In-situ application of biosynthetic nano FeS and bacteria-nano material heterozygote coated by same to Cr removal6+：
a) Directly adding hexavalent chromium (Cr) with the final concentration of 50mg/L6+) Adding into the solution synthesized in the step (4), and measuring Cr in the solution for 1, 2, 5, 10 and 24 hours6+A residual amount;
b) when the solution returns to black, Cr with the final concentration of 50mg/L is added again6+And repeating the process a).
FIG. 5 shows the results of the experiment for reducing hexavalent chromium in situ using a bacteria-nano FeS hybrid in example 1. As can be seen from the figure, the system can realize the high-efficiency and cyclic Cr removal6+. Each time, Cr with a final concentration of 50mg/L was added6+Then, Cr6+Can be rapidly removed, and can achieve a removal rate of over 99% in a 4-cycle experiment for 10 days, and the total concentration of Cr is 200mg/L6+. The result proves that the in-situ utilization of the bacteria-nano FeS heterozygote can efficiently, circularly and sustainably remove Cr in wastewater6+The system has huge performance advantages and practical application potential in practical application.
Example 2
Essentially the same as in example 1, the biosynthetic nano FeS and its coated bacteria-material nano hybrids were used in situ for the treatment of the actual electroplating wastewater:
(1) the basic properties and components of the used electroplating wastewater are as follows: the pH is 1.5, and the pH is strong acid; the contained heavy metals mainly comprise total chromium (1915.7 +/-10.3 mg/L), hexavalent chromium (1532.7 +/-8.7 mg/L), copper (25.5 +/-0.4 mg/L) and zinc (248.3 +/-1.1 mg/L);
(2) in this example, Cr was tested6+In addition to the concentrations, the concentrations of copper and zinc in the systemSimultaneous measurements were also made, with the initial concentrations of each component being 53.67 + -1.13 mg/L, 8.57 + -0.14 and 0.89 + -0.01 mg/L, respectively.
FIG. 6 is a graph showing the change in concentration of major heavy metals when an actual electroplating wastewater was treated with the bacteria-nano FeS hybrid in situ in example 2. As can be seen from the figure, the system can effectively and stably remove Cr6+Meanwhile, the method also has good removal effect on copper and zinc in the wastewater. After 4-period cycle experiment, 97% of Cr can be simultaneously realized6+Removal, 90% copper removal and 88% zinc removal. The result proves that the in-situ utilization of the bacteria-nano FeS heterozygote can be directly applied to the synchronous and efficient removal of various heavy metals in the actual electroplating wastewater, has better stability and sustainability, and provides a good strategy for the treatment of the actual high-concentration heavy metal wastewater.

Claims (10)

1. A preparation method of a FeS nano composite material is characterized by comprising the following steps:
s) under the anaerobic condition, carrying out shake culture on dissimilatory metal reducing bacteria in a culture solution containing water-soluble ferric salt and water-soluble sulfur-containing compounds to obtain the FeS nano composite material.
2. The method according to claim 1, wherein the dissimilatory metal-reducing bacterium is one or more selected from the group consisting of Shewanella onandra, Thioderma thioredoxin, and Aeromonas hydrophila.
3. The preparation method according to claim 1, wherein the water-soluble ferric salt is selected from one or more of ferric chloride, ferric sulfate, ferric ammonium sulfate and ferric citrate; the water-soluble sulfur-containing compound is selected from one or more of thiosulfate, sulfite and sulfide.
4. The preparation method according to claim 1, wherein the step S) is specifically:
dispersing dissimilatory metal reducing bacteria in the culture solution after the deoxidization and sterilization treatment to obtain a bacterial solution;
under the anaerobic condition, adding water-soluble ferric salt and water-soluble sulfur-containing compounds into the bacterial liquid to obtain a culture system, and performing shaking culture to obtain the FeS nano composite material.
5. The method according to claim 4, wherein OD of the bacterial liquid6000.1 to 3.
6. The preparation method according to claim 1, wherein the concentration of the aqueous solution of the ferric iron salt in the culture system is 0.1-10 mmol/L; the concentration of the water-soluble sulfur-containing compound in the culture system is 0.1-10 mmol/L.
7. The method according to claim 1, wherein the temperature of the shaking culture is 4 to 50 ℃; the rotation speed of the shaking culture is 50-250 rpm; the shaking culture time is 5-24 h.
8. The FeS nanocomposite prepared by the preparation method according to any one of claims 1 to 7, which is characterized by comprising dissimilatory metal-reducing bacteria; FeS nano materials are distributed on the cell surface and in the cell membrane of the dissimilatory metal reducing bacteria.
9. The FeS nanocomposite prepared by the preparation method of any one of claims 1 to 7 is applied to treatment of heavy metal-containing wastewater.
10. Use according to claim 9, characterized in that hexavalent chromium ions are included in said heavy metal-containing waste water.
CN202110806646.9A 2021-07-16 2021-07-16 FeS nano composite material, preparation method and application thereof Pending CN113502304A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110806646.9A CN113502304A (en) 2021-07-16 2021-07-16 FeS nano composite material, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110806646.9A CN113502304A (en) 2021-07-16 2021-07-16 FeS nano composite material, preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113502304A true CN113502304A (en) 2021-10-15

Family

ID=78013632

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110806646.9A Pending CN113502304A (en) 2021-07-16 2021-07-16 FeS nano composite material, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113502304A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455692A (en) * 2022-03-08 2022-05-10 南京理工大学 Biological nano hybrid system modified electrode and preparation method and application thereof
CN115181692A (en) * 2022-06-23 2022-10-14 江西师范大学 Ferrous sulfide secondary mineral hybrid and preparation method and application thereof
CN117105394A (en) * 2023-10-23 2023-11-24 江西师范大学 Biological hybrid membrane and preparation method and application thereof
CN118059841A (en) * 2024-04-25 2024-05-24 中南大学 Molecular sieve loaded nano iron sulfide, preparation method thereof and application thereof in mercury removal

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109735527A (en) * 2018-12-29 2019-05-10 江苏大学 A kind of preparation method and applications of Shewanella-nanometer ferrous sulfide capsule
CN111318287A (en) * 2020-02-28 2020-06-23 江苏大学 Biosynthesis method of FeS @ rGO composite material
US20200277211A1 (en) * 2017-09-29 2020-09-03 The Trustees Of Princeton University Oxidant enhanced feammox activity
CN114686401A (en) * 2022-04-14 2022-07-01 华南理工大学 Biological FeS nano particle reinforced microbial agent, preparation method thereof and method for applying biological FeS nano particle reinforced microbial agent to denitrification
US20220332615A1 (en) * 2019-09-25 2022-10-20 West Virginia University Ferric Iron-Dosed Anaerobic Biological Wastewater Treatment Technology

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200277211A1 (en) * 2017-09-29 2020-09-03 The Trustees Of Princeton University Oxidant enhanced feammox activity
CN109735527A (en) * 2018-12-29 2019-05-10 江苏大学 A kind of preparation method and applications of Shewanella-nanometer ferrous sulfide capsule
US20220332615A1 (en) * 2019-09-25 2022-10-20 West Virginia University Ferric Iron-Dosed Anaerobic Biological Wastewater Treatment Technology
CN111318287A (en) * 2020-02-28 2020-06-23 江苏大学 Biosynthesis method of FeS @ rGO composite material
CN114686401A (en) * 2022-04-14 2022-07-01 华南理工大学 Biological FeS nano particle reinforced microbial agent, preparation method thereof and method for applying biological FeS nano particle reinforced microbial agent to denitrification

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
宋渊: "《发酵工程》", 中国农业大学出版社, pages: 77 *
李文卫,俞汉青: "厌氧产能生物技术用于城市污水处理的研究进展", 《ENGINEERING》, vol. 2, no. 4, 15 December 2016 (2016-12-15) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455692A (en) * 2022-03-08 2022-05-10 南京理工大学 Biological nano hybrid system modified electrode and preparation method and application thereof
CN114455692B (en) * 2022-03-08 2024-04-19 南京理工大学 Biological nanometer hybrid system modified electrode and preparation method and application thereof
CN115181692A (en) * 2022-06-23 2022-10-14 江西师范大学 Ferrous sulfide secondary mineral hybrid and preparation method and application thereof
CN117105394A (en) * 2023-10-23 2023-11-24 江西师范大学 Biological hybrid membrane and preparation method and application thereof
CN117105394B (en) * 2023-10-23 2024-02-06 江西师范大学 Biological hybrid membrane and preparation method and application thereof
CN118059841A (en) * 2024-04-25 2024-05-24 中南大学 Molecular sieve loaded nano iron sulfide, preparation method thereof and application thereof in mercury removal

Similar Documents

Publication Publication Date Title
CN113502304A (en) FeS nano composite material, preparation method and application thereof
Chen et al. Enhanced removal of Co (II) and Ni (II) from high-salinity aqueous solution using reductive self-assembly of three-dimensional magnetic fungal hyphal/graphene oxide nanofibers
Tian et al. Enhanced elimination of Cr (VI) from aqueous media by polyethyleneimine modified corn straw biochar supported sulfide nanoscale zero valent iron: Performance and mechanism
Chen et al. Novel magnetic pomelo peel biochar for enhancing Pb (II) and Cu (II) adsorption: performance and mechanism
US11697595B2 (en) Iron-carbon composite material, preparation method thereof and use therefor
Xi et al. Carboxymethyl cellulose stabilized ferrous sulfide@ extracellular polymeric substance for Cr (VI) removal: Characterization, performance, and mechanism
Shi et al. Zero-valent iron mediated biological wastewater and sludge treatment
CN106698582A (en) Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron
Zhao et al. Immobilization of cadmium in river sediment using phosphate solubilizing bacteria coupled with biochar-supported nano-hydroxyapatite
CN108480393B (en) Magnetic aminated hollow microsphere soil remediation agent, and preparation method and application thereof
Liu et al. A win-win solution to chromate removal by sulfidated nanoscale zero-valent iron in sludge
Feng et al. Hydroxyl, Fe2+, and Acidithiobacillus ferrooxidans jointly determined the crystal growth and morphology of schwertmannite in a sulfate-rich acidic environment
Gan et al. Hexavalent chromium remediation based on the synergistic effect between chemoautotrophic bacteria and sulfide minerals
Wang et al. Microalgae-derived carbon quantum dots mediated formation of metal sulfide nano-adsorbents with exceptional cadmium removal performance
Liu et al. Remediation materials for the immobilization of hexavalent chromium in contaminated soil: Preparation, applications, and mechanisms
Wang et al. Biogenic iron mineralization of polyferric sulfate by dissimilatory iron reducing bacteria: Effects of medium composition and electric field stimulation
Zhang et al. Transformation of typical components in anaerobically digested sludge during its conditioning process by KMnO4
Zhang et al. Co-adsorption of tetracycline and Cu (ii) onto a novel amino-functionalized biochar: adsorption behavior and mechanism
Ma et al. Synergistic effects of adsorption and chemical reduction towards the effective Cr (VI) removal in the presence of the sulfur-doped biochar material
Shi et al. Simultaneous heavy metals removal and municipal sewage sludge dewaterability improvement in bioleaching processes by various inoculums
Su et al. Preparation and applications of iron/biochar composites in remediation of heavy metal contaminated soils: Current status and further perspectives
Li et al. Enhanced peroxymonosulfate activation by MoS2/NiCo2S4 composite catalyst for efficient elimination of tetracycline hydrochloride
CN115367818B (en) Preparation method of coagulated sludge-based zero-valent iron biochar dephosphorization composite material
CN114149087B (en) Method for treating arsenic-containing waste liquid by agricultural waste in cooperation with microorganisms
Chen et al. Novel combination of bioleaching and persulfate for the removal of heavy metals from metallurgical industry sludge

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20211015

RJ01 Rejection of invention patent application after publication