CN104046652A - Biosynthesis method of magnetic graphene composite material - Google Patents
Biosynthesis method of magnetic graphene composite material Download PDFInfo
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- CN104046652A CN104046652A CN201410287122.3A CN201410287122A CN104046652A CN 104046652 A CN104046652 A CN 104046652A CN 201410287122 A CN201410287122 A CN 201410287122A CN 104046652 A CN104046652 A CN 104046652A
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Abstract
The invention belongs to the field of biosynthesized nano materials, and relates to a biosynthesis method of a magnetic graphene composite material. The method comprises the following steps: regulating the pH value of 10-30 mmol/L piperazinyl-1,4-diethylsulfonic acid and 10-30 mmol/L sodium lactate to 7.0, deoxidizing and sterilizing; adding graphene oxide into a culture solution, wherein the concentration of the graphene oxide is 0.4-0.6 g/L; carrying out ultrasonic treatment for 30-80 minutes, and adding beta-FeOOH until the concentration of the beta-FeOOH is 30-80 mmol/L; carrying out anaerobic magnetic stirring for 12-36 hours; collecting the dissimilatory metal reducing bacteria in the later logarithmic growth phase; and adding the dissimilatory metal reducing bacteria into the mixed solution, and culturing at 30 DEG C under anaerobic conditions for 132-156 hours to obtain the magnetic graphene composite material. The method has the advantages of mild technical reaction conditions and low energy consumption, and is simple to operate; and the prepared magnetic graphene composite material can be used for adsorption, magnetic catalysis and the like.
Description
Technical field
The invention belongs to biosynthesizing field of nanometer material technology, relate to a kind of biosynthetic means of magnetic graphite alkene matrix material.
Background technology
The features such as Graphene is a kind of Two-dimensional Carbon material that only has an atomic thickness, and to have physical strength high due to it, and specific surface area is large and conduct electricity very well, have broad application prospects in fields such as electronics, sensor, catalysis and the energy.Than the carbon material of other dimensions, Graphene, except having above advantage, also has advantages of that preparation cost is low and is easy to functionalization.Therefore, Graphene becomes the ideal chose of carrying inorganic nano particle.Magnetic Fe
3o
4nano particle has good biocompatibility, superparamagnetism is strong, toxicity is low, be easy to the feature such as easily separated in Preparation and processing, and its application in fields such as catalysis, sensor, drug release and environment remediation is the focus of scientific research always.Therefore, magnetic nanoparticle is loaded on graphene sheet layer and forms magnetic graphite alkene matrix material, can, in conjunction with the advantage of bi-material, improve the use properties of matrix material.The more important thing is, the introducing of magnetic-particle in matrix material, not only can reduce the buildup effect that graphene film interlayer causes due to Van der Waals force, can also realize the separation of grapheme material and reuse; And the introducing at the graphene-based end also can reduce the gathering of magnetic nanoparticle, thus the utilising efficiency of raising magnetic-particle.
The preparation of Graphene and magnetic nano-particle matrix material in recent years with and in the applied research development in the fields such as material, chemistry, biomedicine rapidly.As the people such as Sun H respectively utilize chemical hydrothermal method, covalent bonds method and chemical precipitation method synthesizing magnetic graphene composite material at Journal of Colloid and Interface Science the 363rd volume 98-104 page in 2011 and Zhang H etc. at 14446 pages of papers of delivering of RSC Advances the 4th volume the 14441st – in 2014 people such as Nano Research the 4th volume 550-562 page in 2011, Zhan Y.But these chemical processes are prepared magnetic graphite alkene matrix material, exist that reactions steps is many, the shortcoming such as severe reaction conditions, restive, chemical reagent toxicity height.
Biological process nano materials is the emerging field that cross development gets up gradually along with the progress of the subjects such as nanotechnology, biotechnology and Materials science in recent years.Compare with utilizing traditionally physics and chemistry method nano materials, biological process nano materials has mild condition, environmentally safe, the advantage such as with low cost.In recent years, biosynthesizing magnetic Nano material has been subject to investigator's extensive concern, and has obtained larger progress.The paper reported first that Lovley D R etc. deliver at Nature the 330th volume 252-254 page in 1987 utilize microorganism synthesizing magnetic nano particle.Roh Y etc. report that microorganism utilizes different iron precursor compounds to synthesize Fe at Journal of Microbiology and Biotechnology the 18th volume 1572-1577 page in 2008 and Li X etc. at Applied and Environmental Microbiology the 72nd volume 3236-3244 page in 2006, Lee J H etc. in the paper that Journal of Soils and Sediments the 12nd volume 217-227 page in 2012 is delivered
3o
4magnetic nanoparticle.Simultaneously, biological process synthesizing graphite alkene has also been obtained certain progress, as Salas EC etc. has reported and utilized microorganism to prepare redox graphene at Bioresource Technology the 149th volume 503-508 page in 2013 at Nano Research the 4th volume 563-570 page in 2011 and Liu G etc. at ACS Nano the 4th volume 4852-4856 page in 2010, Wang G etc.But utilize at present microorganism synthesizing magnetic graphene composite material not appear in the newspapers.
Summary of the invention
The object of the invention is to solve magnetic graphite alkene composite material and preparation method thereof severe reaction conditions in prior art, the technical problem that chemical reagent easily pollutes, provides a kind of biological preparation method of magnetic graphite alkene matrix material.
Technical scheme of the present invention is as follows:
A biosynthetic means for magnetic graphite alkene matrix material, concrete steps are as follows:
Step 1: the preparation of graphene oxide: adopt graphene oxide as the synthetic precursor substance of Graphene of magnetic graphite alkene matrix material;
The preparation of step 2: β-FeOOH: adopt β-FeOOH as the synthetic precursor substance of magnetic component of magnetic graphite alkene matrix material;
Step 3: the cultivation of alienation metallic reducing bacterium: the microbial strains that adopts alienation metallic reducing bacterium to prepare magnetic graphite alkene matrix material;
Step 4: the biosynthetic means of magnetic graphite alkene matrix material:
(1) preparation magnetic graphite alkene matrix material nutrient solution: nutrient solution comprises piperazine-Isosorbide-5-Nitrae-bis-ethyl sulfonic acid of 10-30mmol/L and the Sodium.alpha.-hydroxypropionate of 10-30mmol/L, and pH value is adjusted to 7.0, removes oxygen, and sterilizing obtains magnetic graphite alkene matrix material nutrient solution;
(2) preparation graphene oxide and β-FeOOH mixing solutions: the graphene oxide in step 1 is joined in magnetic graphite alkene matrix material nutrient solution, and the concentration of graphene oxide is 0.4-0.6g/L; Ultrasonic 30-80min, then add β-FeOOH, the concentration of β-FeOOH is 30-80mmol/L; Anaerobism magnetic agitation 12-36h, obtains graphene oxide and β-FeOOH mixing solutions;
(3) collect in step 3 in the logarithmic phase alienation metallic reducing bacterium in latter stage;
(4) biosynthesizing of magnetic graphite alkene matrix material: the alienation metallic reducing bacterium of collecting in step 4 (3) is added in the graphene oxide and β-FeOOH mixing solutions of step 4 (2) preparation, under the condition of 30 ℃ of anaerobism, cultivate 132-156h, obtain magnetic graphite alkene matrix material.
Described alienation metallic reducing bacterium is Shewanella oneidensis MR-1.
Described piperazine-Isosorbide-5-Nitrae-bis-ethyl sulfonic acid of step 4 (1) is 20mmol/L, and Sodium.alpha.-hydroxypropionate is 20mmol/L.
The concentration of the graphene oxide that step 4 (2) is described is 0.5g/L, and ultrasonic time is 60min, and the concentration of β-FeOOH is 50mmol/L, and the anaerobism magnetic agitation time is 24h.
The described incubation time of step 4 (4) is 144h.
The invention has the beneficial effects as follows, described magnetic graphite alkene matrix material, can utilize Shewanellaoneidensis MR-1 synthetic at normal temperatures, and magnetic nanoparticle is evenly distributed on graphene sheet layer.The alternative traditional chemical synthesis method of magnetic graphite alkene method for synthesizing composite material involved in the present invention, the feature such as technique has reaction conditions gentleness, energy consumption is low, simple to operate.Magnetic graphite alkene matrix material of the present invention can be realized recycling, and has good application prospect as aspects such as sorbing material and magnetic catalytic materials.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the magnetic graphite alkene matrix material of synthesized.
Fig. 2 is the X-ray diffraction spectrogram of the graphene oxide of synthesized.
Fig. 3 is the X-ray diffraction spectrogram of the magnetic graphite alkene matrix material of synthesized.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, illustrate the specific embodiment of the present invention.
Embodiment 1
The preparation of magnetic graphite alkene matrix material:
(1) preparation of graphene oxide: graphene oxide is the precursor substance of Shewanellaoneidensis MR-1 synthesizing graphite alkene; Take 1g crystalline graphite powder and add in the 46mL vitriol oil and 10mL concentrated nitric acid, ice bath stirs 30min; In concentrated acid Graphite Powder 99 mixed solution, slowly add 6g potassium permanganate, ice bath stirs 120min; Subsequently mixed solution being placed in to 35 ℃ of stirring in water bath spends the night; In mixed solution, add 46mL ultrapure water, 98 ℃ of oil bath 30min, are cooled to normal temperature, then add 200mL ultrapure water; Dropwise adding 20mL massfraction is 30% hydrogen peroxide, to remove excessive potassium permanganate; Products therefrom is washed 3 times with 10% dilute hydrochloric acid, and ultrapure water washing several, until supernatant liquor becomes neutral; Ultrasonic 3h, is deposited in gained in 60 ℃ of vacuum drying ovens and dries after centrifugal, obtains graphene oxide.
(2) preparation of β-FeOOH: β-FeOOH is the synthetic Fe of S.oneidensis MR-1
3o
4precursor substance; The FeCl that the NaOH solution of 10mol/L is dropwise added to 0.4mol/L
36H
2in O solution, the pH that is adjusted to colloid suspension liquid is 7.0, and room temperature is placed 7-8h; By the centrifugal collection of colloid suspension liquid (11000g, 5min) making, and with high purity water washing three times, lead to N
2aeration 30min removes oxygen, obtains β-FeOOH, in 4 ℃ of anaerobism, saves backup.
(3) configuration of biosynthesizing magnetic graphite alkene matrix material nutrient solution: nutrient solution is comprised of piperazine-Isosorbide-5-Nitrae-bis-ethyl sulfonic acid of 20mmol/L and the Sodium.alpha.-hydroxypropionate of 20mmol/L, and pH value is adjusted to 7.0, logical N
2aeration is removed oxygen,
121 ℃ of autoclaving 20min, obtain required biosynthesizing magnetic graphite alkene matrix material nutrient solution.
(4) cultivation of S.oneidensisMR-1: the method is usingd the microbial strains of S.oneidensis MR-1 as synthesizing magnetic graphene composite material; Bacterial classification described in employing Luria-Bertani culture medium culturing, the formula of substratum is: NaCl10g/L, peptone 10g/L, yeast soaks powder 5g/L, with NaOH solution, medium pH is adjusted to 7.0,121 ℃ of autoclaving 20min; S.oneidensis MR-1 is seeded to Luria-Bertani substratum, and inoculative proportion is 1:100; Postvaccinal substratum, at 30 ℃, is cultivated 12h in 150rpm incubator, obtains S.oneidensis MR-1 bacterium liquid.
(5) biosynthetic means of magnetic graphite alkene matrix material:
The 1st step: the graphene oxide of described step (1) is added in the nutrient solution of described step (3), and making graphene oxide concentration is 0.5g/L, ultrasonic dispersion 60min; β-the FeOOH that adds again described step (2), the concentration that makes β-FeOOH is 50mmol/L; Anaerobism magnetic agitation 24h;
The 2nd step: the S.oneidensis MR-1 bacterium liquid centrifugation (11000g of gained after Luria-Bertani culture medium culturing 12h in described step (4), 5min), outwell supernatant liquor, by the cell Eddy diffusion of collecting in piperazine-Isosorbide-5-Nitrae-diethyl sulfonic acid solutions.The concentration of piperazine-Isosorbide-5-Nitrae-diethyl sulfonic acid solutions is 20mmol/L, and this pH is adjusted to 7.0 with NaOH, before use, and under 121 ℃ of conditions, autoclaving 20min; By the thalline centrifugation (11000g, 5min) after suspending, outwell supernatant liquor, the cell that collecting precipitation gets off, three times so repeatedly, this process adds piperazine-1, the object of 4-diethyl sulfonic acid solutions is to clean thalline, to remove remaining Luria-Bertani nutrient media components and meta-bolites;
The 3rd step: the cell of described the 2nd step centrifugation is added in the culture system of described the 1st step and Eddy diffusion, under the condition of 30 ℃ of anaerobism, stir 12h, standing 12h, so circulates twice, keep subsequently standing cultivation 96h, get final product synthesizing magnetic graphene composite material;
The 4th step: the collection of magnetic graphite alkene matrix material; Utilize external magnet separated magnetic graphite alkene matrix material solution described in the 3rd step, remove nutrient solution, add deionized water Eddy diffusion, again separated under the effect of magnet, three times so repeatedly, object is nutrient solution and the remaining thalline of removing described in the 1st step; By magnetic graphite alkene matrix material Eddy diffusion to high purity water; The high purity water that the method is used is logical N before use
2aeration 30min removes oxygen, and 121 ℃, autoclaving 20min; Obtain magnetic graphite alkene matrix material.
Fig. 1 is the transmission electron microscope picture of magnetic graphite alkene matrix material synthetic in embodiment 1, and result shows magnetic Fe
3o
4nano particle loads on graphene sheet layer equably.
Fig. 2 is the X-ray diffraction spectrogram of graphene oxide synthetic in embodiment 1, and in figure, the characteristic peak of graphene oxide appears in 2 θ=9.7 °.
Fig. 3 is the X-ray diffraction spectrogram of magnetic graphite alkene matrix material synthetic in embodiment 1, in spectrogram, the peak of 2 θ=9.7 ° disappears substantially, 23.2 ° there is new weak peak, illustrate that graphene oxide has obtained reduction, 30.3 °, 35.8 °, 43.5 °, 54.3 °, the new peak of 57.5 ° and 63.1 ° appearance illustrates magnetic Fe
3o
4the formation of nano particle.
Claims (8)
1. a biosynthetic means for magnetic graphite alkene matrix material, is characterized in that, concrete steps are as follows:
Step 1: the preparation of graphene oxide: adopt graphene oxide as the synthetic precursor substance of Graphene of magnetic graphite alkene matrix material;
The preparation of step 2: β-FeOOH: adopt β-FeOOH as the synthetic precursor substance of magnetic component of magnetic graphite alkene matrix material;
Step 3: the cultivation of alienation metallic reducing bacterium: the microbial strains that adopts alienation metallic reducing bacterium to prepare magnetic graphite alkene matrix material;
Step 4: the biosynthetic means of magnetic graphite alkene matrix material:
(1) preparation magnetic graphite alkene matrix material nutrient solution: nutrient solution comprises piperazine-Isosorbide-5-Nitrae-bis-ethyl sulfonic acid of 10-30mmol/L and the Sodium.alpha.-hydroxypropionate of 10-30mmol/L, and pH value is adjusted to 7.0, removes oxygen, and sterilizing obtains magnetic graphite alkene matrix material nutrient solution;
(2) preparation graphene oxide and β-FeOOH mixing solutions: the graphene oxide in step 1 is joined in magnetic graphite alkene matrix material nutrient solution, and the concentration of graphene oxide is 0.4-0.6g/L; Ultrasonic 30-80min, then add β-FeOOH, the concentration of β-FeOOH is 30-80mmol/L; Anaerobism magnetic agitation 12-36h, obtains graphene oxide and β-FeOOH mixing solutions;
(3) collect in step 3 in the logarithmic phase alienation metallic reducing bacterium in latter stage;
(4) biosynthesizing of magnetic graphite alkene matrix material: the alienation metallic reducing bacterium of collecting in step 4 (3) is added in the graphene oxide and β-FeOOH mixing solutions of step 4 (2) preparation, under the condition of 30 ℃ of anaerobism, cultivate 132-156h, obtain magnetic graphite alkene matrix material.
2. biosynthetic means according to claim 1, is characterized in that, described alienation metallic reducing bacterium is Shewanella oneidensis MR-1.
3. biosynthetic means according to claim 1 and 2, is characterized in that, described piperazine-Isosorbide-5-Nitrae-bis-ethyl sulfonic acid of step 4 (1) is 20mmol/L, and Sodium.alpha.-hydroxypropionate is 20mmol/L.
4. biosynthetic means according to claim 1 and 2, is characterized in that, the concentration of the graphene oxide that step 4 (2) is described is 0.5g/L, and ultrasonic time is 60min, and the concentration of β-FeOOH is 50mmol/L, and the anaerobism magnetic agitation time is 24h.
5. biosynthetic means according to claim 3, is characterized in that, the concentration of the graphene oxide that step 4 (2) is described is 0.5g/L, and ultrasonic time is 60min, and the concentration of β-FeOOH is 50mmol/L, and the anaerobism magnetic agitation time is 24h.
6. according to the biosynthetic means described in claim 1,2 or 5, it is characterized in that, the described incubation time of step 4 (4) is 144h.
7. biosynthetic means according to claim 3, is characterized in that, the described incubation time of step 4 (4) is 144h.
8. biosynthetic means according to claim 4, is characterized in that, the described incubation time of step 4 (4) is 144h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641632A (en) * | 2017-10-18 | 2018-01-30 | 福州大学 | A kind of method with the carbon-based point of Microbe synthesis |
| CN108424617A (en) * | 2018-03-15 | 2018-08-21 | 厦门大学 | A kind of preparation method and applications of iron oxide hydroxide load graphene oxide fire retardant |
| CN109576310A (en) * | 2018-12-11 | 2019-04-05 | 大连理工大学 | A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material |
| CN113697798A (en) * | 2021-08-11 | 2021-11-26 | 哈尔滨工业大学 | Preparation method of magnetic graphene nano wave absorbing material |
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|---|---|---|---|---|
| WO2014043690A1 (en) * | 2012-09-17 | 2014-03-20 | Musc Foundation For Research Development | Microbial electrosynthetic cells |
| CN103710389A (en) * | 2013-11-25 | 2014-04-09 | 大连理工大学 | Biosynthesis method of magnetic Pd nanocomposite material |
-
2014
- 2014-06-24 CN CN201410287122.3A patent/CN104046652A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014043690A1 (en) * | 2012-09-17 | 2014-03-20 | Musc Foundation For Research Development | Microbial electrosynthetic cells |
| CN103710389A (en) * | 2013-11-25 | 2014-04-09 | 大连理工大学 | Biosynthesis method of magnetic Pd nanocomposite material |
Non-Patent Citations (1)
| Title |
|---|
| EVERETT C. SALAS ET AL: "Reduction of Graphene Oxide via Bacterial Respiration", 《ACS NANO》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641632A (en) * | 2017-10-18 | 2018-01-30 | 福州大学 | A kind of method with the carbon-based point of Microbe synthesis |
| CN108424617A (en) * | 2018-03-15 | 2018-08-21 | 厦门大学 | A kind of preparation method and applications of iron oxide hydroxide load graphene oxide fire retardant |
| CN109576310A (en) * | 2018-12-11 | 2019-04-05 | 大连理工大学 | A kind of method that biological oxidation prepares graphene silicon/iron oxide composite material |
| CN113697798A (en) * | 2021-08-11 | 2021-11-26 | 哈尔滨工业大学 | Preparation method of magnetic graphene nano wave absorbing material |
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Application publication date: 20140917 |