CN109576310A - A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material - Google Patents

A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material Download PDF

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CN109576310A
CN109576310A CN201811509179.8A CN201811509179A CN109576310A CN 109576310 A CN109576310 A CN 109576310A CN 201811509179 A CN201811509179 A CN 201811509179A CN 109576310 A CN109576310 A CN 109576310A
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graphene
composite material
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mother liquor
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CN109576310B (en
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柳广飞
于华莉
周集体
金若菲
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Dalian University of Technology
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Abstract

The invention belongs to biosynthesis technical field of nano material, are related to a kind of method that biological oxidation prepares graphene silicon/iron oxide composite material.The biological synthesis method is the culture of ferrous oxidation bacterium;FeCl2The preparation of mother liquor;The preparation of graphene mother liquor;Utilize the method for biological oxidation synthesizing graphite alkene silicon/iron oxide composite material.The reaction condition of this method is mild, low in cost, easy to operate and environmentally friendly, is a kind of method that green prepares graphene silicon/iron oxide composite material.

Description

A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material
Technical field
The invention belongs to biosynthesis technical field of nano material, specifically a kind of biological oxidation prepares the oxidation of graphene iron The method of object composite material.
Background technique
Graphene be it is a kind of by carbon six-membered ring structure form have high conductivity, bigger serface, high mechanical strength and The nano material of the characteristics such as good chemically and thermally mechanical stability, is widely used in electronics, catalysis and electrochemical energy storage With energy conversion etc. fields.But in application process, graphene platelet may occur serious reunion and accumulate again, this A large amount of losses of effective surface area are normally resulted in, to reduce the performance of graphene.On the other hand, Fe2O3、Fe3O4With The ferriferous oxides such as FeOOH due to good biocompatibility and chemical stability, and it is cheap, toxicity is low, can be used as Sensor, adsorbent and catalyst etc. are widely used in many fields such as electrochemistry, pollutant process and materials synthesis.By iron It the mineral loaded reunion that can effectively alleviate or avoid graphene on graphene and accumulates again, to be provided more for graphene Big surface area and higher adsorption capacity.Therefore, this kind of graphene silicon/iron oxide composite material is with a wide range of applications.
Currently, the preparation of graphene silicon/iron oxide composite material has caused the extensive concern of people.Utilize hydro-thermal point The chemical methodes such as solution, thermal decomposition, chemical precipitation and co-precipitation can prepare graphene ferriferous oxide compound.But these synthesis sides Method needs mostly during the preparation process using toxic or expensive chemical reagent, and some need to also be in the critical conditions such as high temperature or highly basic Lower operation, program is complicated, and operating cost is high, while very likely causing damages to environment.Find green, efficient graphene iron The preparation method of oxide composite is current research hotspot.
Biosynthesis nano material technology refers to that biological utilisation bioactive molecule in the cell or extracellularly close by self assembly It is the novel nano material preparation technology of one kind of rising in recent years at the process of nano material.With traditional preparation method phase Than, mild condition required for the technology, and preparation process cleans, is nontoxic, to more environment-friendly.It is closed currently with bioanalysis Biggish progress, such as Suresh AK are had been achieved in EnvironmentalScience& in 2010 at nano material The 5210-5215 pages of volume 44 of Technology and Ramkumar VS etc. was in Biotechnology Reports the 14th in 2017 It rolls up the paper that the 1-7 pages is delivered and all reports research using Microbe synthesis metal nanoparticle.Meanwhile DongB et al. Graphene-metal is prepared for using microorganism in the 97798-97806 pages paper delivered of volume 5 of RSC Advances in 2015 Composite material.The biosynthesis of current this kind of composite material be mostly using the reducing power of biology by the metal salt of high-valence state also It originally was lower valency metal salt or metal simple-substance.In fact, there is also many in addition to the metal also pathogenic microorganism being widely used Microorganism with metal oxidability, metal or metallic compound can be oxidized to by this quasi-microorganism by lower valency to be had more The metallic compound of high-valence state.Ferrous oxidation bacterium is a kind of typically with the microorganism of oxidisability, energy needed for being grown according to it Source can be divided into two class of photosynthetic autotrophs and chemosynthetic autotroph.Nitrate dependent form ferrous oxidation bacterium is that one kind typicalization can be certainly Type ferrous oxidation bacterium is supported, this kind of bacterium can generate the higher nitrogen intermediate product of nitrite isoreactivity by denitrification process, from And under anaerobic using this kind of nitrogen intermediate product by ferrous oxidation it is the ferriferous oxide of solid phase.KapplerA etc. was in 2005 The 235-245 pages of volume 3 of Geobiology and Larese-Casanova P etc. was in Geochimica et in 2010 The 3721-3734 pages of volume 74 of the Cosmochimica Acta nitrate dependent form ferrous oxidation bacterium reported in environment can oxygen Change Fe (II), and forms ferriferous oxide shell in cell surface and pericentral siphon.It has not yet to see and prepares graphite using ferrous oxidation bacterium The report of alkene silicon/iron oxide composite material.
Using the oxidability synthesizing graphite alkene ferriferous oxide compound of ferrous oxidation bacterium, synthesis process is easy, cleaning, at This is cheap and environmental-friendly.
Summary of the invention
In order to avoid harsh items such as high temperature, highly basic needed for chemical synthesis of graphene silicon/iron oxide composite material process Part, and reduce production process and environment bring is endangered, the present invention provides a kind of utilization microbiological oxidation ability synthetic graphite The features such as method of alkene silicon/iron oxide composite material, this method have reaction condition mild, low in cost, cyclic utilization rate is high.
Technical solution of the present invention:
A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material, the specific steps are as follows:
Step 1: the culture of ferrous oxidation bacterium: being aoxidized using nitrate dependent form ferrous oxidation bacterium as graphene iron is prepared The microorganism fungus kind of object composite material, by cell inoculation in the ineral media containing carbonate buffer solution, inoculation ratio is 5%-10% cultivates 3-5d under 30 DEG C of anaerobic condition;
Step 2:FeCl2The preparation of mother liquor: by FeCl2·4H2O is dissolved in the ultrapure water of anaerobic, and obtaining concentration is 1-2M's FeCl2Mother liquor sterilizing is placed in anaerobism glove box and is sealed under dark condition by mother liquor;
Step 3: the preparation of graphene mother liquor: graphene powder being added in sterile ultrapure water, obtain suspension;It will hang Liquid, which is placed in ultrasonic washing instrument, to be vibrated, to improve the dispersibility of suspension;Suspension after dispersion is by exposing N2(99.999%) it removes The dissolved oxygen in system is removed, the graphene suspension that concentration is 1-2g/L is obtained;
Step 4: utilize the method for biological oxidation ability synthesizing graphite alkene silicon/iron oxide composite material:
(1) the nitrate dependent form ferrous oxidation bacterium of logarithmic growth phase is in incubation step 1;
(2) FeCl prepared by the way that step 2 is added into culture medium2Mother liquor makes initial Fe (II) concentration in culture medium 10mM;After solid phase in system precipitates completely, culture medium is crossed into 0.22 μm of filter membrane under anaerobic, acquisition is clear to contain Fe (II) culture medium, the concentration of residual F e (II) is about initial half in culture medium after film excessively;
(3) different volumes graphene mother liquor, graphene and culture medium is added into the culture medium after the film excessively of step 4 (2) Volume ratio be 1/400-1/10, obtain the ineral media containing various concentration graphene;Under anaerobic by culture medium Stationary culture 3-5h adsorbs Fe (II) sufficiently by graphene;Using the Fe (II) of absorption on the surface of graphene as precursor, pass through Ferrous oxidation bacterium is oxidized as ferriferous oxide, to form graphene silicon/iron oxide composite material;
(4) the ferrous oxidation bacterium bacterium solution that (1) in step 4 is in logarithmic growth phase is added into the culture described in step 4 (3) In base, cell inoculation ratio: 8%, graphene adds concentration: 5-100mg/L, and the concentration that adds by changing graphene regulates and controls to be formed Ferriferous oxide type and content.Stationary culture 5-8d, acquisition biosynthesis in 30 DEG C of anaerobic environment by above-mentioned system Graphene silicon/iron oxide composite material.
The ferrous oxidation bacterium is Acidovorax sp.BoFeN1.
Graphene mother liquor described in step 3 is placed in oscillation 1h or more in ultrasonic washing instrument, to improve the dispersibility of suspension.
The concentration that adds of graphene described in step 4 (3) is 5-100mg/L, according to graphene to add concentration controllable The type and content of the ferriferous oxide of formation;Wherein, when graphene adds concentration between 5-25mg/L, goethite-stone is formed Black alkene composite material;When graphene adds concentration between 50-100mg/L, goethite/lepidocrocite-graphene composite wood is formed Material.
The invention has the advantages that the graphene silicon/iron oxide composite material, can utilize at normal temperature Acidovorax sp.BoFeN1 one-step synthesis, the ferriferous oxide of synthesis crystallization degree with higher, by changing graphene Add concentration, can be selectively formed the mixture of goethite (alpha-feooh) or goethite and lepidocrocite (γ-FeOOH), shape At ferriferous oxide be distributed in graphene surface in corynebacterium, length is between 40-160nm, diameter about 40nm.It is involved in the present invention Graphene silicon/iron oxide composite material the alternative existing chemical synthesis process at present of synthetic method, and reaction condition temperature With, it is low in cost, it is easy to operate, it is environmentally protective.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of synthesized graphene silicon/iron oxide composite material.(a) and (b) is under the different visuals field Goethite-graphene composite material the transmission electron microscope picture observed.
Fig. 2 is synthesized goethite-graphene composite material infrared spectrogram.
Fig. 3 is the X-ray diffractogram of synthesized graphene silicon/iron oxide composite material.(a) be goethite reference substance and Goethite-graphene composite material X-ray diffractogram is (b) that goethite/lepidocrocite-graphene composite material X-ray is spread out Penetrate figure.
Fig. 4 is the high-resolution-ration transmission electric-lens figure of synthesized graphene silicon/iron oxide composite material.(a, b) is goethite- The high-resolution-ration transmission electric-lens figure of graphene composite material, (c, d) are goethite/lepidocrocite-graphene composite material high-resolution Transmission electron microscope picture.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Embodiment 1
Biological oxidation prepares goethite-graphene composite material:
(1) culture of Acidovorax sp.BoFeN1: using Acidovorax sp.BoFeN1 as biosynthesis needle Iron ore-graphene composite material strain;The Spawn incubation is in the ineral media containing 25mM carbonate buffer solution, culture The concrete component of base are as follows: NaHCO32.100g/L MgSO4·7H2O 0.500g/L, NH4Cl 0.300g/L, NaCl 0.200g/ L, NaH2PO40.123g/L, MEM vitamin solution (100 ×) 1mL/L, trace element solution 1mL/L.It is added in the medium 0.41gCH3COONa and 0.85g NaNO3Respectively as the organic substrates and electron acceptor of microorganism growth.First will before culture Vessel required for incubation and liquid transfer gun head high-pressure sterilizing pot sterilize under conditions of 20min at 121 DEG C.It will prepare Culture medium be aerated (N2-CO2Gaseous mixture, volume ratio 80:20) after 30min sealing be placed in the anaerobism glove box after ultraviolet-sterilization (99.999%N2) in, culture medium is crossed into 0.22 μm of moisture film progress degerming and is inoculated with BoFeN1 bacterial strain, inoculation volume ratio is 8%. By the culture medium sealing after inoculation, and in 30 DEG C, dark anaerobic culture box, stationary culture 3-5d is stand-by to logarithmic growth phase.
Wherein, the formula of trace element solution are as follows: nitrilotriacetic acid 1.500g/L, MgSO4·7H2O 3.000g/L, NaCl 1.000g/L MnSO4·H2O 0.500g/L, NH4Cl 0.200g/L, CoSO4·7H2O 0.180g/L, ZnSO4·7H2O 0.180g/L, FeCl2·4H2O 0.100g/L, CaCl2·2H2O 0.100g/L, CuSO4·5H2O 0.010g/L, NiCl2· 6H2O 0.030g/L, Na2SeO3·5H2O 0.030g/L, H3BO30.010g/L, AgNO30.010g/L.Prepare trace element When solution, nitrilotriacetic acid is first added and makes it dissolve, is adjusted after pH is 6.5 with 20%NaOH solution and gradually dissolve other mineral again Salt, it is neutral for adjusting pH with above-mentioned NaOH solution after the completion of preparation.
(2)FeCl2The preparation of mother liquor: 19.8gFeCl is weighed2·4H2O is dissolved in sterile, anaerobic ultrapure water, will be dissolved FeCl afterwards2Mother liquor high-pressure sterilizing pot sterilizes under conditions of 20min at 121 DEG C, obtains the FeCl that concentration is 1M2Mother liquor is set It is sealed under dark condition in anaerobism glove box.
(3) preparation of graphene mother liquor: being added 0.125g graphene powder in the ultrapure water sterile to 100mL, obtains Mother liquor is placed in oscillation 1h or more in ultrasonic washing instrument by the graphene suspension mother liquor of 1.25g/L, to improve suspension dispersibility. Graphene mother liquor after dispersion is aerated (N2-CO2Gaseous mixture, volume ratio 80:20) it seals after 30min, it is placed in anaerobism glove box In it is stand-by.
(4) biological oxidation synthesizes goethite-graphene composite material method:
Step 1: contain 0.41gCH in preparation steps (1)3COONa and 0.85gNaNO3Carbonate buffer-mineral training Base is supported, culture medium is aerated (N2-CO2Gaseous mixture, volume ratio 80:20) it seals after 30min and is placed in anaerobism glove box, detesting FeCl is added in oxygen glove box2Mother liquor makes culture medium initial Fe (II) concentration 10mM, forms the suspension with pale precipitation, Precipitating may be the indissolvable components such as the ferrous carbonate of the anion formation in Fe (II) and solution or ferrous phosphate, in dark condition Lower standing 20h or more, precipitates indissolvable component completely.The suspension is crossed into 0.22 μm of moisture film, acquisition is clear, contains about The ineral media of 5mMFe (II).
Step 2: it is added in the clear ineral media obtained in 30 DEG C of constant temperature of anaerobism glove box to step 1 different The graphene mother liquor mentioned in the step of volume (3) can be obtained the culture medium containing various concentration graphene, graphene concentration Range is between 5-20mg/L.By the culture medium containing graphene in anaerobic culture box stationary culture 3-5h so that in culture medium Fe (II) can sufficiently be adsorbed by graphene.To adsorb Fe (II) on the surface of graphene as the precursor of ferriferous oxide, lead to It crosses BoFeN1 bacterial strain to be oxidized as ferriferous oxide, to form graphene silicon/iron oxide composite material.
Step 3: it after graphene and Fe (II) sufficiently absorption, is cultivated with 8% volume ratio to inoculation of medium step 1 To the BoFeN1 bacterial strain of logarithmic growth phase.Culture medium after inoculation is sealed, the stationary culture 7d under dark condition, is obtained Goethite-graphene composite material of biological oxidation synthesis.
Fig. 1 a and b are the goethite-graphene composite material transmission electron microscope pictures synthesized in embodiment 1, the results showed that are closed At the goethite particle rodlike with nanoscale, for the length of particle between 40-160nm, diameter is 40nm or so.Goethite It is carried on the graphene surface of fold, forms goethite-graphene composite material.
Fig. 2 is that goethite-graphene composite material for synthesizing in graphene, goethite reference substance and embodiment 1 is red External spectrum figure, the results showed that the characteristic group on the composite material of formation containing ferriferous oxide and graphene further proves The successful preparation of this composite material.
Fig. 3 a is compound using ferriferous oxide-graphene synthesized by BoFeN1 bacterial strain in goethite reference substance and embodiment 1 The X-ray diffractogram of material.As seen from the figure composite material 17.8 °, 21.2 °, 33.2 °, 34.7 °, 36.6 °, 40.0 °, Occur the peak type of corresponding goethite at 41.2 °, 53.2 °, 59.0 °, 61.4 ° and 64.0 °, represents graphene out at 24.4 ° Peak, show to form goethite-graphene composite material.
Fig. 4 a and b are goethite-graphene composite material high-resolution-ration transmission electric-lens figures synthesized in embodiment 1.It is logical The spacing of lattice crossed in measurement discovery Fig. 5 b is 0.218nm and 0.245nm, and (140) and (111) for respectively representing goethite are brilliant Face.
Embodiment 2
Biological oxidation prepares goethite/lepidocrocite-graphene composite material:
(1) culture of Acidovorax sp.BoFeN1: using Acidovorax sp.BoFeN1 as biosynthesis needle Iron ore/lepidocrocite-graphene composite material strain;The Spawn incubation is in the ineral media containing 25mM carbonate buffer In, the concrete component of culture medium is the same as example 1 (1).Contain 0.41g CH in the medium3COONa and 0.85g NaNO3Make respectively For the organic substrate and electron acceptor of microorganism.First by vessel required for incubation and liquid transfer gun head high pressure before culture Autoclave sterilizes under conditions of 20min at 121 DEG C.By anaerobism glove box of the prepared culture medium after ultraviolet-sterilization (99.999%N2) in cross 0.22 μm of moisture film and carry out degerming and be inoculated with BoFeN1 bacterial strain, inoculative proportion 8%.By the training after inoculation It supports base and is aerated (N2-CO2Gaseous mixture, volume ratio 80:20) it 30min and seals, it is finally placed in 30 DEG C of constant temperature of anaerobism glove box The stationary culture 3-5d under dark condition, until logarithmic growth phase is stand-by.
(2)FeCl2The preparation of mother liquor: 19.8gFeCl is weighed2·4H2O is dissolved in sterile, anaerobic ultrapure water, will be dissolved FeCl afterwards2Mother liquor high-pressure sterilizing pot sterilizes under conditions of 20min at 121 DEG C, obtains the FeCl that concentration is 1M2Mother liquor, will Mother liquor is placed in anaerobism glove box and is sealed under dark condition.
(3) preparation of graphene mother liquor: being added 0.125g graphene powder in the ultrapure water sterile to 100mL, obtains Mother liquor is placed in oscillation 1h or more in ultrasonic washing instrument by the graphene suspension mother liquor of 1.25g/L, to improve suspension dispersibility. Graphene mother liquor after dispersion is aerated (N2-CO2Gaseous mixture, volume ratio 80:20) it seals after 30min, it is placed in anaerobism glove box In it is stand-by.
(4) biological oxidation synthesizes goethite/lepidocrocite-graphene composite material method:
Step 1: contain 0.41gCH in preparation steps (1)3COONa and 0.85gNaNO3Carbonate buffer-mineral training Base is supported, culture medium is aerated (N2-CO2Gaseous mixture, volume ratio 80:20) it seals after 30min and is placed in anaerobism glove box, detesting FeCl is added in oxygen glove box2Mother liquor makes culture medium initial Fe (II) concentration 10mM, forms the suspension with pale precipitation, Precipitating may be the indissolvable components such as the ferrous carbonate of the anion formation in Fe (II) and solution or ferrous phosphate, in dark condition Lower standing 20h or more, precipitates indissolvable component completely.The suspension is crossed into 0.22 μm of moisture film, acquisition is clear, contains about The ineral media of 5mMFe (II).
Step 2: it is added in the clear ineral media obtained in 30 DEG C of constant temperature of anaerobism glove box to step 1 different The graphene mother liquor mentioned in the step of volume (3) can be obtained the culture medium containing various concentration graphene, graphene concentration Range is between 50-100mg/L.By the culture medium containing graphene in anaerobic culture box stationary culture 3-5h so that culture medium In Fe (II) can sufficiently be adsorbed by graphene.
Step 3: it after graphene and Fe (II) sufficiently absorption, is cultivated with 8% volume ratio to inoculation of medium step 1 To the BoFeN1 bacterial strain of logarithmic growth phase.Culture medium after inoculation is sealed, the stationary culture 7d under dark condition, is obtained Goethite/lepidocrocite-graphene composite material of biological oxidation synthesis.
Fig. 3 b is that ferriferous oxide-graphite that BoFeN1 bacterial strain is synthesized when containing 100mg/LrGO is utilized in embodiment 2 The X-ray diffractogram of alkene composite material.Composite material the 17.8th °, 21.2 °, 33.2 °, 34.7 °, 36.6 °, 40.0 °, The peak for representing goethite at 41.2 °, 53.2 °, 59.0 °, 61.4 ° and 64.0 ° out occurs at the 14.6th °, 25.3 ° and 34.2 ° The peak for representing lepidocrocite, the type for being indicated above the ferriferous oxide of synthesis is the mixture of goethite and lepidocrocite.In addition, compound Material represents the peak of graphene out at the 24.4th °, it was demonstrated that goethite/lepidocrocite-graphene composite material formation.
Fig. 4 c and d are goethite synthesized in embodiment 2/lepidocrocite-graphene composite material high-resolution transmission electricity Mirror figure.It is 0.247nm and 0.252nm by the spacing of lattice in measurement discovery Fig. 4 d, respectively represents (031) crystal face of lepidocrocite With (040) crystal face of goethite.

Claims (5)

1. a kind of method that biological oxidation prepares graphene silicon/iron oxide composite material, which is characterized in that steps are as follows:
Step 1: the culture of ferrous oxidation bacterium: multiple as graphene ferriferous oxide is prepared using nitrate dependent form ferrous oxidation bacterium The microorganism fungus kind of condensation material, by cell inoculation in the ineral media containing carbonate buffer solution, inoculation is than being 5%- 10%, 3-5d is cultivated under 30 DEG C of anaerobic condition;
Step 2:FeCl2The preparation of mother liquor: by FeCl2·4H2O is dissolved in the ultrapure water of anaerobic, obtains the FeCl that concentration is 1-2M2 Mother liquor sterilizing is placed in anaerobism glove box and is sealed under dark condition by mother liquor;
Step 3: the preparation of graphene mother liquor: graphene powder being added in sterile ultrapure water, obtain suspension;Suspension is set It is vibrated in ultrasonic washing instrument;Suspension after dispersion is by exposing N2Dissolved oxygen in removing system, acquisition concentration are 1-2g/L Graphene suspension;
Step 4: utilize the method for biological oxidation ability synthesizing graphite alkene silicon/iron oxide composite material:
(1) the nitrate dependent form ferrous oxidation bacterium of logarithmic growth phase is in incubation step 1;
(2) FeCl prepared by the way that step 2 is added into culture medium2Mother liquor makes initial Fe (II) concentration 10mM in culture medium; After solid phase in system precipitates completely, culture medium is crossed into 0.22 μm of filter membrane under anaerobic, acquisition is clear to contain Fe (II) Culture medium, the concentration for crossing residual F e (II) in culture medium after film is about initial half;
(3) different volumes graphene mother liquor is added into the culture medium after the film excessively of step 4 (2), controls graphene and culture medium Volume ratio between 1/400-1/10, obtain the ineral media containing various concentration graphene;By culture medium in anaerobic condition Lower stationary culture 3-5h adsorbs Fe (II) sufficiently by graphene;Using the Fe (II) of absorption on the surface of graphene as precursor, lead to It crosses ferrous oxidation bacterium to be oxidized as ferriferous oxide, to form graphene silicon/iron oxide composite material;
(4) the ferrous oxidation bacterium bacterium solution that (1) in step 4 is in logarithmic growth phase is added into the culture medium described in step 4 (3) In, cell inoculation ratio: 8%, graphene adds concentration: 5-100mg/L, and the concentration that adds by changing graphene regulates and controls to be formed The type and content of ferriferous oxide;By above-mentioned system in 30 DEG C of anaerobic environment stationary culture 5-8d, obtain biosynthesis Graphene silicon/iron oxide composite material.
2. the method according to claim 1, wherein the ferrous oxidation bacterium is Acidovorax sp.BoFeN1。
3. method according to claim 1 or 2, which is characterized in that it is clear to be placed in ultrasonic wave for graphene mother liquor described in step 3 Oscillation 1h or more in instrument is washed, to improve the dispersibility of suspension.
4. method according to claim 1 or 2, which is characterized in that the concentration that adds of graphene described in step 4 (3) is 5-100mg/L, according to the type and content of the ferriferous oxide for adding the controllable formation of concentration of graphene;Wherein, work as graphene When adding concentration between 5-25mg/L, goethite-graphene composite material is formed;When graphene adds concentration between 50- When 100mg/L, goethite/lepidocrocite-graphene composite material is formed.
5. according to the method described in claim 3, it is characterized in that, the concentration that adds of graphene described in step 4 (3) is 5- 100mg/L, according to the type and content of the ferriferous oxide for adding the controllable formation of concentration of graphene;Wherein, when graphene is thrown When adding concentration between 5-25mg/L, goethite-graphene composite material is formed;When graphene adds concentration between 50-100mg/L When, form goethite/lepidocrocite-graphene composite material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477303A (en) * 2022-01-19 2022-05-13 中山大学 Method for biologically synthesizing magnetic quantum dot ferroferric oxide nano material and application thereof
CN114477303B (en) * 2022-01-19 2023-11-03 中山大学 Method for biosynthesis of magnetic quantum dot ferroferric oxide nano material and application thereof

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