CN109354005A - A kind of porous carbon materials and its preparation method and application prepared using muddy Rhodococcus sp from modification - Google Patents
A kind of porous carbon materials and its preparation method and application prepared using muddy Rhodococcus sp from modification Download PDFInfo
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- CN109354005A CN109354005A CN201811364106.4A CN201811364106A CN109354005A CN 109354005 A CN109354005 A CN 109354005A CN 201811364106 A CN201811364106 A CN 201811364106A CN 109354005 A CN109354005 A CN 109354005A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 48
- 241000316848 Rhodococcus <scale insect> Species 0.000 title claims abstract description 38
- 230000004048 modification Effects 0.000 title claims abstract description 30
- 238000012986 modification Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000001963 growth medium Substances 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000009825 accumulation Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 19
- 239000008103 glucose Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000011534 incubation Methods 0.000 claims description 10
- 230000035508 accumulation Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007836 KH2PO4 Substances 0.000 claims description 7
- 229910018890 NaMoO4 Inorganic materials 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 7
- 229910052564 epsomite Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002054 inoculum Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 239000011686 zinc sulphate Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000007154 intracellular accumulation Effects 0.000 claims description 4
- 229910052603 melanterite Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 241001524101 Rhodococcus opacus Species 0.000 claims 1
- 241000187562 Rhodococcus sp. Species 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 41
- 241000119319 Rhodococcus opacus PD630 Species 0.000 abstract description 24
- 239000007772 electrode material Substances 0.000 abstract description 17
- 239000003990 capacitor Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 25
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000008121 dextrose Substances 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 238000009630 liquid culture Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of porous carbon materials and its preparation method and application prepared using muddy Rhodococcus sp from modification.Ingredient by changing culture medium regulates and controls muddy Rhodococcus sp (Rhodococcus opacus PD630, deposit number DSMZ No.44193) oneself accumulation PHA, it directlys adopt the thallus being collected by centrifugation and carries out carbonization and prepare classifying porous carbon material without any activation step.Bacterium of the invention has abundant pore structure from derivative porous carbon materials are modified.It is used as electrode material for super capacitor, when current density is 0.5A/g, specific volume reaches 256F/g；When current density increases to 20A/g, specific volume remains 206F/g, it is shown that good capacitance and excellent high rate performance.This preparation method has the advantages that novel, easy to operate, preparation cost is low etc., and the material of preparation has the characteristics that be classified aperture, large specific surface area, good conductivity, electrochemical performance, is a kind of ideal supercapacitor or electrode material for battery.
Description
Technical field
The invention belongs to carbon material preparation technical field more particularly to it is a kind of using muddy Rhodococcus sp from modification preparation it is more
Hole carbon material and its preparation method and application.
Background technique
Bacterium has firm cell wall, can remain complete in the environment in rather harsh as prokaryotes
Cell system.Importantly, they are cheap and abundant, it is naturally provided " green " reproducible living resources.Therefore, this
Biology is expected to become for producing the nanometer with some special natures to the biological template of micronsize material slightly, creates
A series of materials with novel feature and characteristic.But using bacterial material as the report of electrode material for super capacitor compared with
Few, Sun (Energy&Environmental Science, 2012,5 (3): 6206-6213.) et al. uses surface of E. coli
Load graphene oxide is simultaneously combined with freezing casting, and then is synthesized with high specific capacitance (1A/g, 327F g-1) it is porous
Carbon.But the preparation process of the porous carbon materials is complicated, condition requires harshness, and bad (5A/g, the 160F g of high rate performance-1)。
The algae that Zhu et al. (Journal of Materials Chemistry A, 2017,6 (4)) is selected by activation of potassium hydroxide
Microballoon synthesized high-performance " green " Carbon-based supercapacitor electrode material shows good chemical property.Although this is porous
The preparation process of absorbent charcoal material is simple, and still, the incubation time of algae is longer to be needed 10 days and need to carry out feed supplement daily, together
When alkali activator have to equipment and stronger corrosivity and cause environmental pollution.Therefore, a kind of simple environmentally protective bacterium is found
Body method of modifying is to prepare high performance porous carbon materials with great scientific meaning and social benefit.
Summary of the invention
To solve the above-mentioned problems, the first purpose of this invention be to provide it is a kind of using muddy Rhodococcus sp from the system of modifying
Standby porous carbon materials；The porous carbon materials have abundant pore structure, large specific surface area, electrochemical performance.
Second object of the present invention is to provide a kind of simple, the environmental-friendly above-mentioned porous carbon materials of preparation method
Preparation method.
Third object of the present invention is to provide a kind of application of above-mentioned porous carbon materials, above-mentioned porous carbon materials is answered
For supercapacitor, high specific capacitance characteristic and excellent high rate performance are shown.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
A kind of porous carbon materials prepared using muddy Rhodococcus sp from modification of the present invention, the porous carbon materials pass through cell
Interior accumulation has the muddy Rhodococcus sp of PHA to obtain through carbonization treatment.
Preferred scheme, the muddy Rhodococcus sp for having PHA that accumulates is cultivated in low nitrogen culture medium by muddy Rhodococcus sp
It obtains.
In the present invention, the low nitrogen refers to that the nitrogen content in low nitrogen culture medium is less than muddy Rhodococcus sp culture arm's length basis
Nitrogen content in culture medium.
Preferred scheme, the concentration of nitrogen source is 0.5-1.2g/L in the low nitrogen culture medium.
As a further preference, the low nitrogen culture medium is minimal medium.
Muddy Rhodococcus sp in the present invention will be conducive to accumulate out PHA when being cultivated using minimal medium, be used for
The nitrogen source of the arm's length basis minimal medium of the Bacteria Culture is 2g/L, and inventor's discovery, which is worked as, is suitably reduced to 0.5- for nitrogen source
1.2g/L can accumulate out PHA, will not influence the normal growth of bacterium, and when the concentration of nitrogen source is lower, although still
It can accumulate out PHA, but the normal growth that bacterium will be inhibited, it is unfavorable for accumulating biomass.
The pioneering work for finding to use intracellular accumulation to have the muddy Rhodococcus sp of PHA that can only modify certainly by bacterium of invention
There are flourishing pore structure, the porous carbon materials of large specific surface area with preparing.
As a further preference, the incubation time is 18-48h.As further preferred, the incubation time
For 22-26h.
Preferred scheme, the specific surface area of the porous carbon materials are 1085~1379m2/g。
Preferred scheme, the specific surface area of the porous carbon materials are 1133~1379m2/g。
Preferred scheme, the muddy Rhodococcus sp are the muddy Rhodococcus sp that deposit number is DSMZ No.44193
Rhodococcus opacus PD630。
A kind of preparation method of the porous carbon materials using muddy Rhodococcus sp from modification preparation of the present invention, including following step
It is rapid:
(1) muddy Rhodococcus sp is inoculated in low nitrogen aseptic culture medium, after culture, is separated by solid-liquid separation, is dry, obtains product；
(2) step (1) products therefrom is placed in carbonization treatment in inert atmosphere, obtains the purified processing of carbonized product, i.e.,
For porous carbon materials.
Muddy Rhodococcus sp is inoculated in low nitrogen aseptic culture medium by technical solution of the present invention, and muddy Rhodococcus sp is in low nitrogen
Condition accumulates itself synthesis PHA (polyhydroxyalkanoate) as intramolecular, and uses this bacterium for accumulating and having PHA, makees
For carbon source synthesising biological carbon, without physics and chemical activating process, can be obtained with rich only by bacterium from modifying
The porous carbon materials of rich pore structure, large specific surface area.Inventor infers, is the PHA due to bacterium intracellular accumulation as high score
The crushing resistance that sub- polyester is equivalent to built-in carbon skeleton enhancing cell prevents the fusion of somatic cells from gathering, while bacterium accumulates
The oxygen content in thallus is improved after PHA, equally distributed oxygen-containing group (carbonyl, hydroxyl) is advantageous in carbonisation in PHA
The specific capacity of carbon material is improved in forming hole, and increases the wetability of carbon material, so that can get most has excellent electrochemical
The porous carbon materials of energy.
Preferred scheme, in step (1), the condition of culture of the muddy Rhodococcus sp is that inoculum concentration 2-10% (moves into seed
The ratio of nutrient solution volume after the volume and inoculation of liquid), 25-40 DEG C of temperature, natural pH condition, incubation time 18-48h.
As a further preference, the incubation time is 22-26h.
Inventors have found that the incubation time of bacterium has very big shadow for the subsequent structure for being formed by porous carbon materials
It rings, incubation time is too long too short, and the specific surface area of resulting porous carbon materials all will be substantially lower than gained in the solution of the present invention
Porous carbon materials specific surface area, inventor has found that PHA is opened from 10 hours after microbionation by fluorescence microscope
Begin accumulation, reach maximum value in 20 hours accumulations, subsequent PHA starts to be consumed by bacterium as carbon source, on day 4 when PHA it is several
It is depleted.This fills part and illustrates that the accumulation of the Forming Mechanism dependence of porous carbon materials in the present invention has oneself of the bacterium of PHA
Modification.
But inventor's discovery is not optimal incubation time, due to reaching when accumulation reaches maximum value
When to maximum value, consumption just slowly starts, but biomass is also incrementally increasing, when such as culture 24 hours, PHA product
The tired apparent biomass simultaneously that reduces of nothing of measuring increased much relative to 20 hours, was at this time just that PHA content and biomass are maximum
The case where change, therefore preferred incubation time of the invention is 22~26 hours.
Preferred scheme, in step (1), the low nitrogen aseptic culture medium is using glucose as the sterile culture of sole carbon source
Base, ingredient are glucose 5g/L, NH4Cl0.5-1.2g/L、MgSO4·7H2O 1.0g/L、CaCl2·2H2O0.015g/L、
CoCl2·6H2O0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·7H2O 0.50mg/L、
H3BO3 0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·7H2O0.40mg/L、
FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
Preferred scheme, in step (1), the mode of the separation of solid and liquid is centrifuge separation, and the revolving speed of centrifuge separation is
6000~8000rpm.
Preferred scheme, in step (1), the drying mode is vacuum freeze drying to constant weight.
Preferred scheme, in step (2), the temperature of the carbonization treatment is 700-900 DEG C, and the time of carbonization treatment is 1-
3h, heating rate are 2-5 DEG C/min.
As a further preference, in step (2), the temperature of the carbonization treatment is 800-900 DEG C, carbonization treatment when
Between be 1-2h.
Preferred scheme, in step (2), the inert atmosphere is nitrogen atmosphere or argon atmosphere.
Preferred scheme, in step (2), the process of the purified treatment are as follows: by carbonized product successively using hydrochloric acid, go
Ionized water is cleaned to neutrality；In 50-80 DEG C of dry 8-12h up to porous carbon materials.
A kind of application of the porous carbon materials using muddy Rhodococcus sp from modification preparation of the present invention, by the porous carbon
Material is applied to supercapacitor.
Present invention has an advantage that
(1) work for finding to use intracellular accumulation to have the bacterium of PHA that can only modify certainly by bacterium that the present invention is pioneering
There is abundant pore structure with preparing, the porous carbon materials of large specific surface area, using microorganism as raw material, greatly
The added value of natural products is increased, the bacterial growth period is short, physics and chemical activating process are not necessarily to from after modifying using bacterium,
Condition is easily-controllable, simple process and low cost, environmental-friendly, opens new, the suitable big rule of industry for the preparation of porous carbon materials
The process route of mould production.
(2) at present using bacterium from method of modifying improve its derived carbon chemical property and for supercapacitor there has been no
Relevant report.The specific surface area of porous carbon prepared by the present invention is between 1085~1379m2Between/g, there is abundant hole
Structure.
(3) bacterium modifies thallus porous carbon electrode material for super capacitor, under the current density of 0.5A/g, specific volume certainly
256F/g can be reached, its specific volume reaches 206F/g under the current density of 20A/g, show excellent high rate performance, while
Specific capacitance still keeps 90% or more after 3000 circulations under the current density of 20A/g, has good cyclical stability.
(4) due to good electrochemical energy storage ability, high specific capacitance, excellent high rate performance and without poison ring
The characteristics of guarantor, therefore have as efficient, lightweight porous carbon electrode material in Novel super capacitor electrode material technical field
Have wide practical use.
Make furtherly below with reference to technical effect of the attached drawing to design of the invention, specific material structure and generation
It is bright, to fully understand the purposes, features and effects of the present invention.
Detailed description of the invention
Fig. 1: the embodiment of the present invention 1 cultivates the muddy Rhodococcus sp fluorogram of resulting accumulation PHA.
Fig. 2: the bacterium that the unmodified thallus porous carbon (a) of comparative example 1 of the present invention prepares with the embodiment of the present invention 1 spreads out from modification
Transmission electron microscope (SEM) figure of raw porous carbon (b)；
Fig. 3: bacterium prepared by the embodiment of the present invention 1 prepares not from the derivative porous carbon electrode material of modification and comparative example 1
The cyclic voltammetry curve of modified bacteria porous carbon electrode material.
Fig. 4: bacterium prepared by the embodiment of the present invention 1 prepares not from the derivative porous carbon electrode material of modification and comparative example 1
The constant current charge-discharge curve of modified bacteria porous carbon electrode material.
Fig. 5: bacterium prepared by the embodiment of the present invention 1 prepares not from the derivative porous carbon electrode material of modification and comparative example 1
The AC impedance curve of modified bacteria porous carbon electrode material.
Specific embodiment
Present invention is further described in detail in the following with reference to the drawings and specific embodiments, but not as to limit of the invention
It is fixed.
Embodiment 1
(1) the Rhodococcus opacus PD630 thallus for being stored in the inclined-plane LB is inoculated in LB liquid medium,
At a temperature of 30 DEG C, 18h is cultivated, the seed liquor of Rhodococcus opacus PD630 is obtained；The wherein LB Liquid Culture
Each composition proportion of base are as follows: peptone 10g, yeast powder 5g, sodium chloride 10g, distilled water 1L；The inclined-plane LB is in above-mentioned formula
On the basis of be added 15g/L agar；
(2) the obtained Rhodococcus opacus PD630 seed liquor of previous step is centrifuged 5 under the conditions of 8000rpm
Minute, supernatant liquor is discarded, thallus is collected；
(3) by the Rhodococcus opacus PD630 thallus of collection by 2% inoculum concentration (move into seed liquor volume and
The ratio of nutrient solution volume after inoculation), it is inoculated in low nitrogen dextrose culture-medium, at a temperature of 30 DEG C, natural pH is cultivated for 24 hours,
8000rpm is centrifugally separating to obtain microorganism；Wherein low each composition proportion of nitrogen dextrose culture-medium are as follows: glucose 5g/L,
NH4Cl0.5g/L、MgSO4·7H2O 1.0g/L、CaCl2·2H2O0.015g/L、CoCl2·6H2O 0.050mg/L、CuCl2·
2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·7H2O 0.50mg/L、H3BO3 0.015mg/L、MnSO4·H2O
0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·7H2O0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O
2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
(4) the obtained Rhodococcus opacus PD630 thallus of previous step is placed in vacuum freeze drier extremely
Constant weight obtains dry thallus.
(5) dry thallus is placed in tube furnace, in a nitrogen atmosphere, is stopped with the heating rate of 5 DEG C/min in 900 DEG C
Stay 2h, be naturally cooling to wash products therefrom with dilute hydrochloric acid and deionized water after room temperature, until solution pH value be 7,
By gained sediment, dry 12h obtains bacterium from the derivative porous carbon of modification under conditions of 80 DEG C.
The specific surface area of obtained porous carbon is 1379m by the implementation of the present embodiment2/g。
The bacterium of the accumulation PHA cultivated through this embodiment after dyeing fluorogram as shown in Figure 1, display is entire
Bacterial cell is colored, it is seen that PHA can be largely accumulated under the condition of culture of the present embodiment.
The SEM result of obtained porous carbon materials is as shown in Figure 2 through this embodiment, it is seen that bacterium is more from derivative is modified
Hole carbon has pore structure abundant.
Nickel foam (1 is coated to after the electrode material, binder and conductive carbon black are ground uniformly according to the ratio of 8:1:1
× 1cm) on (70 DEG C) are dried, working electrode is made, under three-electrode system (platinized platinum be used as to electrode, Hg/HgO electrode
As reference electrode, the KOH aqueous solution of 6M is as electrolyte), test can be carried out to its electrochemistry.
Fig. 3 is that this example prepares the cyclic voltammetry curve of electrode and comparative example in the case where 50mV/s sweeps speed, and Fig. 4 is this example system
For electrode and comparative example to electrode material after the visible bacterium of constant current charge-discharge curve under the current density of 0.5A/g is modified certainly
Capacitive property be obviously improved.
Fig. 5 is the AC impedance curve that this example prepares electrode Yu comparative example electrode, as a result visible bacterium electricity from after modifying
The internal resistance of pole material is substantially reduced, and promotes electric double layer effect.According to the electrode of this example preparation in different current densities
Under constant current charge-discharge curve, be calculated the combination electrode current density be 0.5A/g under, specific capacitance is up to 256F/g；When
When current density increases to 20A/g, capacitance value 206F/g, capacitance fade is smaller, can retain 80% capacitor, performance
Excellent high rate performance is gone out.
Cyclic voltammetry curve is measured under three-electrode system, this bacterium derives porous carbon super capacitor from modification as the result is shown
Device electrode material has good cyclical stability, and specific capacitance is still kept after 3000 circulations under the current density of 20A/g
95% or more.
Embodiment 2
(1) seed liquor of Rhodococcus opacus PD630 is obtained by step (1), (2) culture in embodiment 1.
(2) obtained Rhodococcus opacus PD630 seed liquor is centrifuged 5 minutes under the conditions of 8000rpm, is abandoned
Supernatant liquor is removed, thallus is collected；
(3) the Rhodococcus opacus PD630 thallus of collection is pressed into 10% inoculum concentration, is inoculated in low nitrogen glucose
In culture medium, at a temperature of 30 DEG C, natural pH cultivates 48h, and 8000rpm is centrifugally separating to obtain microorganism；The wherein low nitrogen
Each composition proportion of dextrose culture-medium are as follows: glucose 5g/L, NH4Cl0.8g/L、MgSO4·7H2O 1.0g/L、CaCl2·
2H2O0.015g/L、CoCl2·6H2O 0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·
7H2O 0.50mg/L、H3BO3 0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·
7H2O0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
(4) the obtained Rhodococcus opacus PD630 thallus of previous step is placed in vacuum freeze drier extremely
Constant weight obtains dry thallus.
(5) dry thallus is placed in tube furnace, in a nitrogen atmosphere, is stopped with the heating rate of 5 DEG C/min in 700 DEG C
Stay 3h, be naturally cooling to wash products therefrom with dilute hydrochloric acid and deionized water after room temperature, until solution pH value be 7,
By gained sediment, dry 12h obtains bacterium from the derivative porous carbon of modification under conditions of 80 DEG C.
The specific surface area of obtained porous carbon is 1085m by the implementation of the present embodiment2/g。
Test can be carried out to its electrochemistry using method same as Example 1.The porous carbon electrodes are in current density
For under 0.5A/g, specific capacitance is up to 228F/g；When current density increases to 20A/g, capability value 196F/g, capacitor declines
Subtract smaller, 85% capacitor can be retained, show excellent high rate performance.
Embodiment 3
(1) seed liquor of Rhodococcus opacus PD630 is obtained by step (1), (2) culture in embodiment 1.
(2) obtained Rhodococcus opacus PD630 seed liquor is centrifuged 5 minutes under the conditions of 8000rpm, is abandoned
Supernatant liquor is removed, thallus is collected；
(3) the Rhodococcus opacus PD630 thallus of collection is pressed into 5% inoculum concentration, is inoculated in low nitrogen glucose training
It supports in base, at a temperature of 30 DEG C, natural pH, for 24 hours, 8000rpm is centrifugally separating to obtain microorganism for culture；The wherein Portugal Di Dan
Each composition proportion of grape sugar culture-medium are as follows: glucose 5g/L, NH4Cl1.2g/L、MgSO4·7H2O 1.0g/L、CaCl2·
2H2O0.015g/L、CoCl2·6H2O 0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·
7H2O 0.50mg/L、H3BO3 0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·
7H2O0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
(4) the obtained Rhodococcus opacus PD630 thallus of previous step is placed in vacuum freeze drier extremely
Constant weight obtains dry thallus.
(5) dry thallus is placed in tube furnace, in a nitrogen atmosphere, is stopped with the heating rate of 5 DEG C/min in 800 DEG C
Stay 1h, be naturally cooling to wash products therefrom with dilute hydrochloric acid and deionized water after room temperature, until solution pH value be 7,
By gained sediment, dry 12h obtains bacterium from the derivative porous carbon of modification under conditions of 80 DEG C.
The specific surface area of obtained porous carbon is 1133m by the implementation of the present embodiment2/g。
Test can be carried out to its electrochemistry using method same as Example 1.The porous carbon electrodes are in current density
For under 0.5A/g, specific capacitance is up to 246F/g；When current density increases to 20A/g, capability value 204F/g, capacitor declines
Subtract smaller, 83% capacitor can be retained, show excellent high rate performance.
Comparative example 1
The porous carbon preparation method that this comparative example is related to uses normal nitrogen content culture medium, and bacterium does not accumulate under this condition
PHA, the specific steps are as follows:
(1) the Rhodococcus opacus PD630 thallus for being stored in the inclined-plane LB is inoculated in LB liquid medium,
At a temperature of 30 DEG C, 18h is cultivated, the seed liquor of Rhodococcus opacus PD630 is obtained；The wherein LB Liquid Culture
Each composition proportion of base are as follows: peptone 10g, yeast powder 5g, sodium chloride 10g, distilled water 1L；The inclined-plane LB is in above-mentioned formula
On the basis of be added 15g/L agar；
(2) the obtained Rhodococcus opacus PD630 seed liquor of previous step is centrifuged 5 under the conditions of 8000rpm
Minute, supernatant liquor is discarded, thallus is collected；
(3) the Rhodococcus opacus PD630 of collection is pressed into 2% inoculum concentration, is inoculated in normal nitrogen content glucose
In culture medium, at a temperature of 30 DEG C, natural pH, for 24 hours, 8000rpm is centrifugally separating to obtain microorganism for culture；It is wherein described normal
Each composition proportion of nitrogen content dextrose culture-medium are as follows: glucose 5g/L, NH4Cl 2g/L、MgSO4·7H2O 1.0g/L、
CaCl2·2H2O0.015g/L、CoCl2·6H2O 0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、
FeSO4·7H2O 0.50mg/L、H3BO3 0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、
ZnSO4·7H2O0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4
1.33g/L。
(4) the obtained Rhodococcus opacus PD630 thallus of previous step is placed in vacuum freeze drier extremely
Constant weight obtains dry thallus.
(5) dry thallus is placed in tube furnace, in a nitrogen atmosphere, is stopped with the heating rate of 5 DEG C/min in 900 DEG C
Stay 2h, be naturally cooling to wash products therefrom with dilute hydrochloric acid and deionized water after room temperature, until solution pH value be 7,
By gained sediment, dry 12h obtains unmodified bacterial derivation porous carbon under conditions of 80 DEG C.
It is 162m through porous carbon specific surface area obtained by this comparative example2/ g derives porous carbon from modification far below bacterium
(~1199m2/g).Fig. 2 is the SEM figure of the derivative porous carbon of unmodified thallus prepared by comparative example, it can be seen that material surface
Smooth hole is seldom.
Test can be carried out to its electrochemistry using method same as Example 1.In the case where current density is 0.5A/g, than
Capacitor is that 46F/g is below embodiment (~241F/g).The AC impedance curve that Fig. 5 is shown also indicates that comparative example electrode material phase
There is bigger internal resistance for embodiment.As a result explanation can be obviously improved by the bacterium that regulation nitrogen source is realized from modification
Its specific surface area, cellular structure and electrochemical properties for deriving porous carbon.
Comparative example 2
(1) seed liquor of Rhodococcus opacus PD630 is obtained by step (1), (2) culture in embodiment 1.
(2) obtained Rhodococcus opacus PD630 seed liquor is centrifuged 5 minutes under the conditions of 8000rpm, is abandoned
Supernatant liquor is removed, thallus is collected；
(3) the Rhodococcus opacus PD630 thallus of collection is pressed into 10% inoculum concentration, is inoculated in low nitrogen glucose
In culture medium, at a temperature of 30 DEG C, natural pH cultivates 96h, and 8000rpm is centrifugally separating to obtain microorganism；The wherein low nitrogen
Each composition proportion of dextrose culture-medium are as follows: glucose 5g/L, NH4Cl0.5g/L、MgSO4·7H2O 1.0g/L、CaCl2·
2H2O0.015g/L、CoCl2·6H2O 0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·
7H2O 0.50mg/L、H3BO3 0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·
7H2O0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
(4) the obtained Rhodococcus opacus PD630 thallus of previous step is placed in vacuum freeze drier extremely
Constant weight obtains dry thallus.
(5) dry thallus is placed in tube furnace, in a nitrogen atmosphere, is stopped with the heating rate of 5 DEG C/min in 900 DEG C
Stay 2h, be naturally cooling to wash products therefrom with dilute hydrochloric acid and deionized water after room temperature, until solution pH value be 7,
By gained sediment, dry 12h obtains bacterium from the derivative porous carbon of modification under conditions of 80 DEG C.
It is 731m through porous carbon specific surface area obtained by this comparative example 22/ g is far below embodiment (~1199m2/g).It adopts
Test can be carried out to its electrochemistry with method same as Example 1.In the case where current density is 0.5A/g, specific capacitance is
153F/g is lower than embodiment (~241F/g).The result shows that the PHA accumulated into the cell makes the property of derived carbon after being consumed by bacterium
Can be substantially reduced, it was demonstrated that be bacterium accumulation PHA modification improve its derive specific surface area of porous carbon, cellular structure and
Electrochemical properties.
Claims (10)
1. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification, it is characterised in that: the porous carbon materials pass through
Intracellular accumulation has the muddy Rhodococcus sp of PHA to obtain through carbonization treatment.
2. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification according to claim 1, it is characterised in that: institute
The muddy Rhodococcus sp that stating accumulation has PHA is to cultivate acquisition in low nitrogen culture medium by muddy Rhodococcus sp.
3. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification according to claim 2, it is characterised in that: institute
The concentration for stating nitrogen source in low nitrogen culture medium is 0.5-1.2g/L.
4. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification according to claim 1 or claim 2, feature are existed
In: the muddy Rhodococcus sp is the muddy Rhodococcus sp Rhodococcus opacus that deposit number is DSMZ No.44193
PD630。
5. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification according to claim 1 or 2, feature are existed
In: the porous carbon materials specific surface area is 1085~1379m2/g。
6. preparation is a kind of as claimed in any one of claims 1 to 5, wherein to utilize the muddy Rhodococcus sp porous carbon that certainly prepared by modification
The method of material, which comprises the following steps:
(1) muddy Rhodococcus sp is inoculated in low nitrogen aseptic culture medium, after culture, is separated by solid-liquid separation, is dry, obtains product；
(2) step (1) products therefrom is obtained into the purified processing of carbonized product, as in being placed in carbonization treatment in inert atmosphere
Porous carbon materials.
7. a kind of preparation method of porous carbon materials using muddy Rhodococcus sp from modification preparation according to claim 6,
It is characterized by: the condition of culture of the muddy Rhodococcus sp is inoculum concentration 2-10%, 25-40 DEG C of temperature, natural in step (1)
PH condition, incubation time 18-48h.
8. a kind of preparation method of porous carbon materials using muddy Rhodococcus sp from modification preparation according to claim 6,
It is characterized by: in step (1), the low nitrogen aseptic culture medium be using glucose as the aseptic culture medium of sole carbon source, at
It is divided into glucose 5g/L, NH4Cl0.5-1.2g/L、MgSO4·7H2O 1.0g/L、CaCl2·2H2O0.015g/L、CoCl2·
6H2O 0.050mg/L、CuCl2·2H2O0.0050mg/L、EDTA 0.25mg/L、FeSO4·7H2O 0.50mg/L、H3BO3
0.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·7H2O 0.40mg/L、FeNa-
EDTA 5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO42.14g/L KH2PO4 1.33g/L。
9. a kind of preparation method of porous carbon materials using muddy Rhodococcus sp from modification preparation according to claim 6,
It is characterized by: in step (1), the mode of the separation of solid and liquid is centrifuge separation, the revolving speed of centrifuge separation is 6000~
8000rpm；
In step (1), the drying mode is vacuum freeze drying to constant weight；
In step (2), the temperature of the carbonization treatment is 700-900 DEG C, and the time of carbonization treatment is 1-3h, heating rate 2-
5℃/min；
In step (2), the inert atmosphere is nitrogen atmosphere or argon atmosphere.
10. a kind of porous carbon materials prepared using muddy Rhodococcus sp from modification described in any one according to claim 1~5
Application, it is characterised in that: by the porous carbon materials be applied to supercapacitor.
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