CN106430162B - The preparation method of graphene hydrogel - Google Patents
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
Abstract
The preparation method of graphene hydrogel, is related to graphene.The following steps are included: 1) prepare graphene oxide suspension；2) selection and preculture of strain；3) culture solution is prepared；4) culture solution deoxygenation sterilizes；5) graphene oxide suspension is added；6) inoculation of strain；7) formation of graphene hydrogel.Simple process, reaction condition is milder, and raw material is easy to get, low in cost, is suitble to low cost, large-scale industrial production.Make it possible the interaction of viable bacteria and graphene oxide, the graphene hydrogel of preparation, contain water complex in bean curd shape black, graphene oxide after containing microorganism and being reduced, retain the amphipathic of graphene oxide, it can be applied in water phase very well, while increase anti-load-bearing capacity of the thallus in water body by the package action of graphene, be the compound of a kind of viable bacteria and graphene.
Description
Technical field
The present invention relates to graphenes, more particularly to the preparation method of graphene hydrogel.
Background technique
From two-dimensional material graphene in 2004 by after independent removed, graphene is moved as most thin in history, most tough, electronics
The high new material of shifting rate, causes people greatly to pay close attention to.Each carbon atom of graphene is sp2Hydridization passes through sp2Hydridization
Unimolecule honeycomb lamellar structure made of carbon atom is connected with each other, makes it have high specific surface area, can load various
Molecule；And each carbon atom contributes a remaining p orbital electron to form big pi bond, and pi-electron can move freely, and impart stone
The excellent electric conductivity of black alkene, while graphene also has excellent mechanical property and thermal property, therefore graphene is in super electricity
Container, battery, display, ultralight aircraft materials, flak jackets, biomedicine field have important potential using value.
But very strong π-π interaction between two-dimensional graphene lamella, be easy to promote two-dimensional graphene synusia reunite and
It stacks, material property is caused to decline.Conversely, connecting the two-dimensional graphene of monolithic to form three-dimensional structure, graphene can be made
Property it is more stable, and three-dimensional grapheme is more favorable to be modified, and it is more extensive new that purposes is formed in conjunction with other materials
Type composite material, such as three-dimensional grapheme hydrogel.In general, hydrogel is being physically or chemically crosslinked by single polymer chain
The polymer network of formation can largely absorb water and not dissolve in water.Hydrogel is this to have solid and liquid double grading concurrently
Property is allowed to have the application to become more and more important in the fields such as drug loading and release, high hydroscopic resin, pollutant absorption, sensing,
Graphene hydrogel also becomes research hotspot (Hu little Hong, Ma little Han, Duo Yaru, Zhang Xinyan, Liu Tianyu, Zhao Yao, Cai in recent years
A kind of super graphene oxide-hydrogel composite drug carrier of outstanding [P] China, 2013:CN103272239A).
Currently, the method for preparing graphene has: mechanical stripping method, vapour deposition process, cutting carbon nanotubes method and oxidation are also
Former method etc., wherein oxidation-reduction method yield is higher, is suitble to large-scale production, is to prepare the most common method of graphene at present.
For graphene oxide other than the carbon atom benzene ring structure containing graphene, edge and inside are also rich in big
The oxygen-containing groups such as epoxy group, carboxyl, carbonyl, the hydroxyl of amount are the important pioneers of one kind of graphene-structured, itself are also one kind
The derivative of two-dimensional graphene, being modified to its functional group also makes the property of graphene oxide become multiplicity.By graphite oxide
Alkene is reduced to graphene and usually requires using toxic reducing agent such as hydrazine, or the reaction condition harsh using high temperature etc., seeks
Green, safe and efficient, low energy consumption preparation method becomes key (Zhang Suling, Du of graphite alkenes new material large-scale application
The preparation of Zhuo, Li Gongke graphite oxide and graphene and its application [J] the analysis test journal in sample pre-treatments,
2012,31 (9): 1178-1183).
Although grapheme material is by attention, the research about graphene and microbial interaction relationship is seldom, benefit
Being prepared graphene with micro-reduction graphene oxide and composite material is made in microorganism and graphene is even more to be rarely reported,
Some researchs even show under specific condition to have inhibition killing effect to microorganism by graphene that (Lu little Ju, Li Shaozhen, Meng mandarin duck are old
Along life, Yang Xiangyu, Liu Junming poly- amino ester-graphene oxide anti-bacterial hydrogel and preparation method thereof [P] is Chinese, and 2016:
CN105348793A)。
Summary of the invention
It is an object of the invention in view of the above-mentioned problems existing in the prior art, provide a kind of preparation of graphene hydrogel
Method.
The present invention the following steps are included:
1) graphene oxide suspension is prepared；
In step 1), the specific method of the preparation graphene oxide suspension can are as follows: by crystalline flake graphite and KMnO4It is mixed
It closes, adds the mixed acid solution of sulfuric acid and phosphoric acid, heated at constant temperature, liquid to be mixed are cooled to room temperature in water-bath after reaction
Afterwards, it pours into the ice water containing hydrogenperoxide steam generator, after it is golden yellow that solution is by green and brown discoloration, successively with hydrochloric acid, ethyl alcohol and goes
Ion water washing, until graphene oxide suspension is solidified after can not being centrifuged with ether, then being washed with deionized water to pH is neutrality,
It is ultrasonically formed graphene oxide suspension；
The crystalline flake graphite of 300 mesh can be used in the crystalline flake graphite；The crystalline flake graphite, KMnO4, sulfuric acid, phosphoric acid, contain peroxide
The proportion of the ice water, ether of changing hydrogen solution can be 3.0g ︰ 18.0g ︰ 360mL ︰ 40mL ︰ 400mL ︰ 200mL, wherein crystalline flake graphite,
KMnO4Calculated by mass, in terms of volume, the sulfuric acid can be used for sulfuric acid, phosphoric acid, the ice water containing hydrogenperoxide steam generator, ether
In the ice water containing hydrogenperoxide steam generator, 3mL hydrogenperoxide steam generator, mistake is can be used in the sulfuric acid that mass percentage concentration is 98%
The mass percentage concentration of hydrogen peroxide solution can be 30%；The temperature of the reaction can be 35~40 DEG C；It is described permanent in water-bath
The temperature of temperature heating can be 50 DEG C, and the time of heated at constant temperature can be 12h；It is described successively to be washed with hydrochloric acid, ethyl alcohol and deionized water
It can successively be washed 8~20 times with salt acid elution 3~5 times, ethanol washing 2~3 times, deionized water；The condition of the ultrasound can be
400W ultrasound 4h；The dispersion concentration of the graphene oxide suspension can be 7~9g/L.
2) selection and preculture of strain；
In step 2), the strain can be selected from one of commercially available Shewanella, commercially available ground bacillus etc., can also be used certainly
The strain after mixed bacterium or sludge sewage domestication in right water body (such as seawater, lake water)；The commercially available Shewanella
(Shewanella putrefaciens) is purchased from China General Microbiological culture presevation administrative center (CGMCC), preservation number:
1.6515；The commercially available ground bacillus (Geobacter sulfurreducens Caccavo et al.ATCC 51573) is commercially available
From Beijing Central Plains company；The fine oxygen activation culture of the commercially available Shewanella, commercially available ground bacillus to the logarithmic phase later period uses, pure bacterium
Training method be ordinary culture medium (LB, TSB etc.) 10~14h of shaking table culture.
3) culture solution is prepared；
In step 3), the formula of the culture solution includes carbon source, nitrogen source, inorganic salts, 10 microelement of SL and vitamin
Solution；The inorganic salts include NaCl, KCl, CaCl2、MgCl2·6H2O、KH2PO4、NaHCO3、NaSO4；
The optimization formula of the culture solution can be (g/L): NH4Cl 0.1~1, NaCl 0.5~2, KCl 0.1~1,
CaCl20.05~0.2, MgCl2·6H2O 0.05~0.2, KH2PO40.1~0.5, NaHCO31~5, NaSO40.05~
0.2, CH310 0.5~2mL of microelement of COONa 0.5~2, SL, 5~15mL of vitamin solution, solvent is deionized water；
The carbon source removes CH3The common organic carbon source of microorganism can also be used in COONa, and the organic carbon source can be selected from carbon source
The common organic carbon source of the Anaerobic culturels such as carbohydrate, volatile organic acids, methanol, glucose etc. can be used in the carbon source carbohydrate, described
Propionic acid or butyric acid etc. can be used in volatile organic acids；
The nitrogen source removes NH4(NH can also be used in Cl4)2SO4, the common nitrogen source such as peptone；
The composition of 10 microelement of SL can be (g/L): FeCl2·4H2O 0.5~2.5, CoCl2·6H2O 0.1
~0.3, MnCl4·4H2O 0.05~0.2, ZnCl20.02~0.1, H3BO30.01~0.1, Na2MoO4·2H2O 0.01~
0.05, NiCl6·H2O 0.01~0.05, CuCl2·2H2O 0.005~0.05, another addition 0~20mL of 25%HCl adjust molten
Liquid pH is 7, and solvent is deionized water；
The composition of the vitamin solution can be (mg/L): biotin 0.01~0.1, folic acid 0.005~0.05, pyridoxol
0.05~0.5, riboflavin 0.01~0.1, thiamine 0.05~0.2, vitamin b12 0.5~0.2, niacinamide 0.1~1 is right
Aminobenzoic acid 0.1~1, lipoic acid 0.01~0.1, pantothenic acid 0.01~0.1, solvent are deionized water.
KH in the inorganic salts2PO4K can be used2HPO4Instead of NaSO4FeSO can be used4·7H2O、KSO4, FeS replace.
4) culture solution deoxygenation sterilizes；
In step 4), the specific method of the culture solution deoxygenation sterilizing can are as follows: is added in the serum bottle of each 125mL
80mL culture solution then passes to the N for being 80% containing mass percent2The CO for being 20% with mass percent2Gaseous mixture, in liquid level
It is aerated 20min under lower aeration 25min, liquid level of jumping a queue, is aerated 15min on liquid level of jumping a queue, culture solution is made to remove oxygen, subsequent serum
Aluminium lid high pressure steam sterilization 20min at 121 DEG C on bottle fastener.
5) graphene oxide suspension is added；
In step 5), the specific method of the addition graphene oxide suspension can are as follows: stone will be aoxidized obtained by step 1)
Black alkene suspension sterilizes 2h under ultraviolet light irradiation, with 5mL syringe in the N for being 80% containing mass percent2With quality percentage
Than the CO for 20%2It evacuates in mixture pipe at least 1 time, the oxygen in Inside Syringe, is then handled to through step 4) repeatedly
3~5mL graphene oxide dispersion is injected in serum bottle culture solution afterwards, is mixed.
6) inoculation of strain；
In step 6), the specific method of the inoculation of the strain can are as follows: irradiates syringe under super-clean bench ultraviolet lamp
Then 20min takes out bacterium solution obtained by step 2), 1 ︰ 10 injects 8mL bacterium solution into step 5) gained serum bottle by volume, mixes
It is even.
7) formation of graphene hydrogel.
In step 7), the specific method of the formation of the gel can are as follows: and anaerobism serum bottle obtained by step 6) is put into 20~
Sealing and standing culture in 40 DEG C of incubator forms graphene hydrogel after culture 10 days.
Graphene oxide is reduced, and becomes dark solution from brown yellow solution, surface occurs gauffer curling, gradually rolls into a ball
It is poly-, thallus is tightly wrapped up wherein, bacterium finally obtains bean curd using the graphene oxide after reduction as attachment point flourish
Shape black graphene hydrogel.Simple process of the invention, reaction condition is milder, and is omitted commonly used in the prior art
Poisonous and hazardous reducing agent, raw material are easy to get, low in cost, are suitble to low cost, large-scale industrial production.Without using toxic examination
Agent, it is simple and easy, so that the interaction of viable bacteria and graphene oxide is become possibility, the hydrogel of preparation can be used as a kind of new
Type composite material is introduced to the market.Graphene hydrogel prepared by the present invention contains water complex in bean curd shape black, contains micro- life
Object and the graphene oxide after being reduced.
The graphene hydrogel that the present invention obtains, includes fluid nutrient medium, microorganism, reproducibility graphene oxide,
Middle microorganism can be the bacterium in mixed bacterium such as activated sludge, natural water body, be also possible to pure bacterium such as Shewanella, ground bacillus
Deng reproducibility graphene oxide is partly or entirely to be restored graphene oxide by the reduction of microorganism.The water-setting
Glue retains the amphipathic of graphene oxide, can be applied in water phase very well, while so that thallus is existed by the package action of graphene
Anti- load-bearing capacity in water body increases, and is the compound of a kind of viable bacteria and graphene.
Detailed description of the invention
Fig. 1 is the electron microscope that hydrogel is made in embodiment 2, and microorganism is attached to graphene layer on piece.
Fig. 2 is the electron microscope that hydrogel is made in embodiment 2, and microorganism and graphene form compound.
Fig. 3 is the XRD diagram before and after 2 graphene oxide plastic of embodiment, GO: graphene oxide before reacting, Lake-rGO: warp
Graphene oxide after lake water micro-reduction.
Fig. 4 is the FTIR figure before and after 2 graphene oxide plastic of embodiment, GO: reacts preceding graphene oxide, Lake-rGO:
Graphene oxide after lake water micro-reduction.
Specific embodiment
Following embodiment will be further elaborated with the present invention in conjunction with attached drawing.
Embodiment 1:
A kind of process preparing graphene hydrogel using Shewanella.Include the following steps:
By Shewanella strain, (Shewanella putrefaciens Shewanella putrefaciens, is purchased from China General Microbiological
Culture presevation administrative center (CGMCC) preservation number: 1.6515) accesses the training of LB liquid after carrying out activation culture on LB plate again
Feeding base is activated, into growth logarithmic phase.
After culture solution is prepared according to table 1 (trace element solution and vitamin solution formula are shown in Table 2 and 3 respectively),
Adjusting culture solution pH is 7, and packing carries out aeration deoxygenation to serum bottle, carries out autoclave sterilization after deoxygenation.
By the high-purity crystalline flake graphite 3.0g of 300 mesh and 18.0g KMnO4Mixing, while 98% concentrated sulfuric acid containing 360mL is added
With the mixed acid solution of 40mL phosphoric acid, stirring, control exothermic heat of reaction is 37 DEG C, and then heated at constant temperature is stirred in 50 DEG C of water-bath
Mix 12h.
After liquid to be mixed is cooled to room temperature, mixed liquor is poured into the ice water of 400mL 30% hydrogenperoxide steam generator containing 3mL.
After solution is golden yellow by green and brown discoloration, with dilute hydrochloric acid wash 3 times, ethanol washing 2 times, deionized water wash 10
It is secondary, until graphene oxide suspension is solidified after can not being centrifuged with 200mL ether, 4 times are washed with deionized water after solidification again to pH
It is 7, forms graphene oxide suspension, dispersion concentration 8.38g/L in 400W ultrasound 4h.
According to the graphene oxide suspension concentration of production, the graphene oxide suspension that suitable volumes are added enters culture
Base, control graphene oxide are 0.37g/L in the concentration of culture medium.8mL Shewanella bacterium solution is added according to volume ratio 1:10
In culture medium, mix.
It is put into 28 DEG C of incubators and cultivates 10 days, graphene water-setting gum forming.
1 Media Components of table
2 Trace Elements of table
3 vitamin composition of table
A kind of embodiment 2: graphene hydrogel being prepared using bacterium is mixed in lake water.
Using the preparation method of embodiment 1, the difference is that microbe inoculation is commercially available ground bacillus (Geobacter
Sulfurreducens Caccavo et al.ATCC 51573) it is purchased from Beijing Central Plains company, it is cultivated in 37 DEG C of incubators
10 days, form graphene hydrogel.
The electron microscopic picture of gel shows that microorganism is attached to graphene layer on piece (Fig. 1), surface occur gauffer curling, by
Gradually reunite, thallus is tightly wrapped up wherein, graphene oxide forms graphene as attachment point flourish after bacterium will restore
Compound (Fig. 2).By hydrogel after ultrasonication, through dilute hydrochloric acid, ethanol washing, then it is washed with deionized water twice, puts
It is freeze-dried after entering -80 DEG C of refrigerator freezings, then carries out the gel characterization for removing microorganism, demonstrate,proved by XRD characterization (Fig. 3)
Bright, 10 ° of graphene oxide or so of appearance disappears after reduction, and the disappearance of oxygen-containing functional group, institute are proved by FTIR spectrogram (Fig. 4)
It is restored during forming gel by microbial portion with graphene oxide.
Claims (5)
1. the preparation method of graphene hydrogel, it is characterised in that the following steps are included:
1) graphene oxide suspension is prepared: by crystalline flake graphite and KMnO4Mixing, adds the mixed acid solution of sulfuric acid and phosphoric acid,
Heated at constant temperature is poured into the ice water containing hydrogenperoxide steam generator after liquid to be mixed is cooled to room temperature in water-bath after reaction, when molten
It after liquid is golden yellow by green and brown discoloration, is successively washed with hydrochloric acid, ethyl alcohol and deionized water, until graphene oxide suspension can not
It is solidified after centrifugation with ether, then being washed with deionized water to pH is neutrality, is ultrasonically formed graphene oxide suspension；
2) selection and preculture of strain, the strain are mixed in commercially available Shewanella, commercially available ground bacillus, natural water
One of strain after bacterium, sludge sewage domestication；The natural water is seawater or lake water；It is described commercially available uncommon
Watt Salmonella (Shewanella putrefaciens) is purchased from China General Microbiological culture presevation administrative center (CGMCC), saves
Number: 1.6515；The commercially available ground bacillus is purchased from Beijing Central Plains company；The commercially available Shewanella, the aerobic activation of commercially available ground bacillus
Culture to the logarithmic phase later period uses, and the training method of pure bacterium uses 10~14h of LB culture medium or TSB culture medium shaking table culture；
3) culture solution, the formula of the culture solution are as follows: NH are prepared4Cl 0.1~1g/L, NaCl 0.5~2g/L, KCl 0.1~
1g/L, CaCl20.05~0.2g/L, MgCl2·6H2O 0.05~0.2g/L, KH2PO40.1~0.5g/L, NaHCO31~
5g/L, NaSO40.05~0.2g/L, CH310 0.5~2mL of microelement of COONa 0.5~2g/L, SL, vitamin solution 5~
15mL, solvent are deionized water；
4) culture solution deoxygenation sterilizes: 80mL culture solution being added in the serum bottle of each 125mL, then passes to containing mass percent
For 80% N2The CO for being 20% with mass percent2Gaseous mixture, be aerated under liquid level 25min, be aerated under liquid level of jumping a queue 20min,
It jumps a queue and is aerated 15min on liquid level, culture solution is made to remove oxygen, subsequent serum bottle buckles aluminium lid high pressure steam sterilization at 121 DEG C
20min；
5) it adds graphene oxide suspension: graphene oxide suspension obtained by step 1) is sterilized 2h under ultraviolet light irradiation,
With 5mL syringe in the N for being 80% containing mass percent2The CO for being 20% with mass percent2It is evacuated to repeatedly in mixture pipe
Few 1 time, the oxygen in Inside Syringe, then 3~5mL of injection aoxidizes stone in through step 4) treated serum bottle culture solution
Black alkene dispersion liquid mixes；
6) inoculation of strain；
7) formation of graphene hydrogel.
2. the preparation method of graphene hydrogel as described in claim 1, it is characterised in that the crystalline flake graphite uses 300 purposes
Crystalline flake graphite；The crystalline flake graphite, KMnO4, sulfuric acid, phosphoric acid, the ice water containing hydrogenperoxide steam generator, ether proportion be 3.0g ︰
18.0g ︰ 360mL ︰ 40mL ︰ 400mL ︰ 200mL, wherein crystalline flake graphite, KMnO4Calculated by mass, sulfuric acid, contains peroxidating at phosphoric acid
The ice water of hydrogen solution, ether in terms of volume, the sulfuric acid use mass percentage concentration for 98% sulfuric acid, it is described to contain peroxidating
In the ice water of hydrogen solution, using 3mL hydrogenperoxide steam generator, the mass percentage concentration of hydrogenperoxide steam generator is 30%；The reaction
Temperature be 35~40 DEG C；The temperature of the heated at constant temperature in water-bath is 50 DEG C, and the time of heated at constant temperature is 12h；It is described
It is successively washed with hydrochloric acid, ethyl alcohol and deionized water and is successively washed with salt acid elution 3~5 times, ethanol washing 2~3 times, deionized water
8~20 times；The condition of the ultrasound is 400W ultrasound 4h；The dispersion concentration of the graphene oxide suspension is 7~9g/L.
3. the preparation method of graphene hydrogel as described in claim 1, it is characterised in that the composition of the SL10 microelement
Are as follows: FeCl2·4H2O 0.5~2.5g/L, CoCl2·6H2O 0.1~0.3g/L, MnCl4·4H20.05~0.2g/L of O,
ZnCl20.02~0.1g/L, H3BO30.01~0.1g/L, Na2MoO4·2H2O 0.01~0.05g/L, NiCl6·H2O 0.01
~0.05g/L, CuCl2·2H20.005~0.05g/L of O, another 0~20mL of 25%HCl adjusting pH value of solution that is added is 7, and solvent is
Deionized water；The composition of the vitamin solution are as follows: 0.01~0.1mg/L of biotin, 0.005~0.05mg/L of folic acid, pyrrole are trembled
0.05~0.5mg/L of alcohol, 0.01~0.1mg/L of riboflavin, 0.05~0.2mg/L of thiamine, 0.5~0.2mg/ of vitamin b12
L, 0.1~1mg/L of niacinamide, 0.1~1mg/L of p-aminobenzoic acid, 0.01~0.1mg/L of lipoic acid, pantothenic acid 0.01~
0.1mg/L, solvent are deionized water.
4. the preparation method of graphene hydrogel as described in claim 1, it is characterised in that in step 6), the strain is connect
Kind method particularly includes: syringe is irradiated into 20min under super-clean bench ultraviolet lamp, then bacterium solution obtained by step 2) is taken out, is pressed
Bacterium solution and nutrient solution volume injection 8mL bacterium solution, mixing into step 5) gained serum bottle than 1 ︰ 10.
5. the preparation method of graphene hydrogel as described in claim 1, it is characterised in that in step 7), the shape of the gel
At method particularly includes: the anaerobism serum bottle after step 6) to be accessed to strain is put into sealing and standing in 20~40 DEG C of incubator and trains
It supports, forms graphene hydrogel after culture 10 days.
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