CN109354005B - Porous carbon material prepared by utilizing self-modification of rhodococcus turbinatus as well as preparation method and application of porous carbon material - Google Patents
Porous carbon material prepared by utilizing self-modification of rhodococcus turbinatus as well as preparation method and application of porous carbon material Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
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- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 239000011686 zinc sulphate 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 6
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- 239000012298 atmosphere Substances 0.000 claims description 4
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- 241000894006 Bacteria Species 0.000 abstract description 28
- 239000007772 electrode material Substances 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 11
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- 239000000463 material Substances 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 6
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- 230000004913 activation Effects 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 230000001580 bacterial effect Effects 0.000 description 24
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- 230000000694 effects Effects 0.000 description 7
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
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- 239000002028 Biomass Substances 0.000 description 4
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- 108010080698 Peptones Proteins 0.000 description 2
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 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
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- 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
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- 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
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- 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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- Materials Engineering (AREA)
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a porous carbon material prepared by utilizing self-modification of rhodococcus turbinatus, and a preparation method and application thereof. PHA is accumulated by Rhodococcus rhodochrous (Rhodococcus opacus PD630, deposit number DSMZ No.44193) through regulating and controlling the components of a culture medium, and the thalli collected by centrifugation is directly carbonized without any activation step to prepare the hierarchical porous carbon material. The bacteria self-modification derived porous carbon material has a rich pore structure. When the nano-silver nano-particles are used as electrode materials of a super capacitor, the specific volume of the nano-particles reaches 256F/g when the current density is 0.5A/g; when the current density is increased to 20A/g, the specific volume is kept at 206F/g, and good capacitance and excellent rate capability are shown. The preparation method has the advantages of novelty, simple operation, low preparation cost and the like, and the prepared material has the characteristics of graded aperture, large specific surface area, good conductivity and excellent electrochemical performance, and is an ideal electrode material for a super capacitor or a battery.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a porous carbon material prepared by utilizing rhodococcus turbinatus self-modification, and a preparation method and application thereof.
Background
Bacteria, as prokaryotes, have a robust cell wall that maintains an intact cellular system even in relatively harsh environments. Importantly, they are cheap and abundant, a "green" renewable biological resource that is provided naturally. Therefore, these microorganisms are expected to become biological templates for the production of nanometer to micrometer sized materials with some specific properties, creating a range of materials with novel features and characteristics. But do notThe reports of using bacterial materials as electrode materials of super capacitors are less, Sun (Energy)&Environmental Science,2012,5(3):6206--1) Porous carbon of (2). However, the preparation process of the porous carbon material is complex, the condition requirement is strict, and the rate capability is not good (5A/g, 160F g)-1). Zhu et al (Journal of Materials Chemistry A,2017,6(4)) synthesize high-performance green carbon-based supercapacitor electrode Materials by activating selected algae microspheres with potassium hydroxide, and show good electrochemical performance. Although the preparation process of the porous activated carbon material is simple, the culture time of the algae is longer and needs 10 days, and the supplement is needed every day, and meanwhile, the alkali activator has strong corrosiveness on equipment and causes environmental pollution. Therefore, the method for preparing the high-performance porous carbon material by finding a simple green and environment-friendly thallus modification method has great scientific significance and social benefit.
Disclosure of Invention
In order to solve the above problems, a first object of the present invention is to provide a porous carbon material prepared by self-modification using rhodococcus turbinatus; the porous carbon material has rich pore structure, large specific surface area and excellent electrochemical performance.
The second object of the present invention is to provide a method for preparing the above porous carbon material, which is simple and environmentally friendly.
The third purpose of the invention is to provide an application of the porous carbon material, wherein the porous carbon material is applied to a super capacitor and shows high specific capacitance characteristic and excellent rate capability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a porous carbon material prepared by utilizing rhodococcus turbinatus self-modification, which is obtained by carbonizing rhodococcus turbinatus accumulated with PHA in cells.
Preferably, the PHA-accumulated Rhodococcus turbinatus is obtained by culturing Rhodococcus turbinatus in a low-nitrogen medium.
In the invention, the low nitrogen means that the nitrogen content in the low nitrogen culture medium is less than that in a normal basic culture medium for culturing rhodococcus turbinatus.
Preferably, the concentration of the nitrogen source in the low-nitrogen medium is 0.5-1.2 g/L.
Further preferably, the low nitrogen medium is an inorganic salt medium.
The rhodococcus turbinatus is beneficial to accumulating PHA when being cultured by adopting an inorganic salt culture medium, the nitrogen source of a normal basic inorganic salt culture medium for culturing the bacteria is 2g/L, the inventor finds that the PHA can be accumulated without influencing the normal growth of the bacteria when the nitrogen source is properly reduced to 0.5-1.2g/L, and the PHA can be accumulated but the normal growth of the bacteria can be inhibited when the concentration of the nitrogen source is lower, so that the biomass accumulation is not facilitated.
The invention initially discovers that the rhodococcus turbinatus accumulated with PHA in cells can be used for preparing the porous carbon material with developed pore structure and large specific surface area only through the effect of bacterial self-modification.
Further preferably, the culture time is 18 to 48 hours. More preferably, the culture time is 22 to 26 hours.
Preferably, the specific surface area of the porous carbon material is 1085-1379 m2/g。
Preferably, the specific surface area of the porous carbon material is 1133-1379 m2/g。
Preferably, the Rhodococcus turbinatus is Rhodococcus Rhodococcus opacus PD630 deposited under DSMZ No. 44193.
The invention relates to a preparation method of a porous carbon material prepared by utilizing self-modification of rhodococcus turbinatum, which comprises the following steps:
(1) inoculating the rhodococcus turbinatus in a low-nitrogen sterile culture medium, and after culturing, carrying out solid-liquid separation and drying to obtain a product;
(2) and (2) putting the product obtained in the step (1) into an inert atmosphere for carbonization treatment, and purifying the obtained carbonized product to obtain the porous carbon material.
According to the technical scheme, rhodococcus turbinatus is inoculated into a low-nitrogen sterile culture medium, the rhodococcus turbinatus synthesizes PHA (polyhydroxyalkanoate) by itself under the low-nitrogen condition to be used as an intramolecular accumulation, the bacteria with the accumulated PHA are used as a carbon source to synthesize biochar, and the porous carbon material with rich pore structures and large specific surface area can be obtained only through the self-modification of the bacteria without physical and chemical activation processes. The inventor concludes that since PHA accumulated in bacterial cells as a high molecular polyester corresponds to a built-in carbon skeleton to enhance the anti-pressure property of cells to prevent the fusion and aggregation of bacterial cells, and the bacteria accumulate PHA to increase the oxygen content in the bacterial cells, the uniformly distributed oxygen-containing groups (carbonyl and hydroxyl) in PHA are beneficial to forming pores during carbonization to increase the specific capacity of the carbon material and increase the wettability of the carbon material, thereby obtaining the porous carbon material with the most excellent electrochemical performance.
Preferably, in the step (1), the culture condition of the rhodococcus turbinatus is that the inoculation amount is 2-10% (the ratio of the volume of the seed solution transferred to the volume of the culture solution after inoculation), the temperature is 25-40 ℃, the natural pH condition is adopted, and the culture time is 18-48 h.
Further preferably, the culture time is 22 to 26 hours.
The inventor finds that the culture time of the bacteria has great influence on the structure of the porous carbon material formed subsequently, the culture time is too long and too short, the specific surface area of the obtained porous carbon material is greatly lower than that of the porous carbon material obtained in the scheme of the invention, and the inventor finds that PHA is accumulated from 10 hours after the inoculation of the bacteria through the observation of a fluorescence microscope, the accumulated amount reaches the maximum value in 20 hours, then PHA is used as a carbon source and is consumed by the bacteria, and the PHA is almost consumed at the 4 th day. This fully demonstrates the self-modifying effect of PHA-accumulating bacteria upon which the mechanism of formation of the porous carbon material in the present invention is dependent.
However, the inventors found that the culture time is not optimal when the accumulation amount reaches the maximum, since the consumption is slowly started when the accumulation amount reaches the maximum, but the biomass is gradually increased, for example, when the culture is carried out for 24 hours, the accumulation amount of PHA is not obviously reduced, and the biomass is greatly increased relative to 20 hours, and the PHA content and the biomass are maximized, so the culture time is preferably 22-26 hours.
Preferably, in step (1), the low-nitrogen sterile medium is a sterile medium containing glucose as a sole carbon source and contains 5g/L, NH of glucose4Cl0.5-1.2g/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。
In the preferable scheme, in the step (1), the solid-liquid separation mode is centrifugal separation, and the rotating speed of the centrifugal separation is 6000-8000 rpm.
Preferably, in the step (1), the drying manner is vacuum freeze drying to constant weight.
Preferably, in the step (2), the temperature of the carbonization treatment is 700-900 ℃, the time of the carbonization treatment is 1-3h, and the temperature rise speed is 2-5 ℃/min.
As a further optimization, in the step (2), the temperature of the carbonization treatment is 800-900 ℃, and the time of the carbonization treatment is 1-2 h.
Preferably, in the step (2), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
Preferably, in the step (2), the purification treatment process is as follows: washing the carbonized product to be neutral by hydrochloric acid and deionized water in sequence; drying at 50-80 deg.C for 8-12h to obtain porous carbon material.
The invention relates to application of a porous carbon material prepared by utilizing self-modification of rhodococcus turbinatus, and the porous carbon material is applied to a super capacitor.
The invention has the advantages that:
(1) the invention initially discovers that the porous carbon material with rich pore structure and large specific surface area can be prepared by adopting the bacteria with PHA accumulated in cells only through the action of bacterial self-modification, the additional value of natural products is greatly increased by taking bacterial thalli as a raw material, the growth period of the bacteria is short, the physical and chemical activation processes are not needed after the bacterial self-modification, the conditions are easy to control, the process is simple, the cost is low, the environment is friendly, and a new process route which is suitable for industrial large-scale production is opened up for the preparation of the porous carbon material.
(2) At present, no relevant report is available for improving the electrochemical performance of the derived carbon by adopting a bacterial self-modification method and applying the electrochemical performance to a super capacitor. The specific surface area of the porous carbon prepared by the method is 1085-1379 m2Between/g, has a rich pore structure.
(3) The specific volume of the electrode material of the bacterial self-modified porous carbon supercapacitor can reach 256F/g under the current density of 0.5A/g, the specific volume of the electrode material can reach 206F/g under the current density of 20A/g, excellent rate performance is shown, meanwhile, the specific capacitance can still be kept above 90% after 3000 times of circulation under the current density of 20A/g, and the electrode material has good circulation stability.
(4) The porous carbon electrode material has the characteristics of good electrochemical energy storage capacity, high specific capacitance, excellent rate performance, no toxicity and environmental friendliness, so that the porous carbon electrode material has a wide application prospect in the technical field of novel supercapacitor electrode materials as a high-efficiency and light-weight porous carbon electrode material.
The conception, specific material structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the objects, features and effects of the present invention.
Drawings
FIG. 1: the fluorescence spectrum of the PHA-accumulated rhodococcus turbinatus cultured in the example 1 of the invention.
FIG. 2: a transmission electron microscope (SEM) image of the non-modified porous carbon (a) of the comparative example 1 and the self-modified porous carbon (b) of the bacteria prepared in the example 1;
FIG. 3: cyclic voltammetry curves of the bacterial self-modified derivative porous carbon electrode material prepared in example 1 of the invention and the unmodified bacterial porous carbon electrode material prepared in comparative example 1.
FIG. 4: the porous carbon electrode material derived from the self-modified bacteria prepared in the embodiment 1 of the invention and the unmodified porous carbon electrode material prepared in the comparative example 1 have constant current charge-discharge curves.
FIG. 5: the alternating current impedance curves of the porous carbon electrode material derived from the self-modified bacteria prepared in the example 1 of the invention and the porous carbon electrode material of the unmodified bacteria prepared in the comparative example 1 are shown.
Detailed Description
The invention is described in further detail below with reference to the figures and the examples, but without limiting the invention.
Example 1
(1) Inoculating Rhodococcus opacus PD630 bacteria stored on an LB inclined plane into an LB liquid culture medium, and culturing at 30 ℃ for 18h to obtain a seed solution of the Rhodococcus opacus PD 630; wherein the LB liquid culture medium comprises the following components in percentage by weight: 10g of peptone, 5g of yeast powder, 10g of sodium chloride and 1L of distilled water; the LB inclined plane is formed by adding 15g/L agar on the basis of the formula;
(2) centrifuging the Rhodococcus opacus PD630 seed solution obtained in the last step for 5 minutes at 8000rpm, discarding the supernatant, and collecting the thallus;
(3) inoculating the collected Rhodococcus opacus PD630 thallus into a low-nitrogen glucose culture medium according to the inoculation amount of 2% (the ratio of the volume of the transferred seed liquid to the volume of the culture liquid after inoculation), culturing at the temperature of 30 ℃ and natural pH for 24h, and performing centrifugal separation at 8000rpm to obtain bacterial thallus; the low-nitrogen glucose culture medium comprises the following components in parts by weight: 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；K2HPO4 2.14g/L，KH2PO4 1.33g/L。
(4) Putting the Rhodococcus opacus PD630 thallus obtained in the last step into a vacuum freeze dryer to constant weight to obtain dry thallus.
(5) And (2) placing the dried thalli in a tubular furnace, standing at 900 ℃ for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, naturally cooling to room temperature, washing the obtained product with dilute hydrochloric acid and deionized water until the pH value of the solution is 7, and drying the obtained precipitate at 80 ℃ for 12h to obtain the bacterial self-modifying derivative porous carbon.
The specific surface area of the porous carbon prepared by the practice of this example was 1379m2/g。
The stained fluorescence spectrum of the PHA-accumulating bacteria cultured in this example is shown in FIG. 1, which shows that the whole bacterial cells are stained, and it can be seen that PHA can be accumulated in large quantities under the culture conditions of this example.
The SEM result of the porous carbon material prepared in this example is shown in fig. 2, which shows that the bacteria self-modification derived porous carbon has a rich pore structure.
The electrode material, the binder and the conductive carbon black are uniformly ground according to the ratio of 8:1:1, then coated on foamed nickel (1 x 1cm) to be dried (70 ℃) to prepare a working electrode, and the electrochemical performance of the working electrode is tested under a three-electrode system (a platinum sheet is used as a counter electrode, a Hg/HgO electrode is used as a reference electrode, and 6M KOH aqueous solution is used as electrolyte).
FIG. 3 is a cyclic voltammetry curve of the electrode prepared in the example and the comparative example at a sweep rate of 50mV/s, and FIG. 4 is a constant current charging and discharging curve of the electrode prepared in the example and the comparative example at a current density of 0.5A/g, which shows that the capacitance performance of the electrode material is obviously improved after the self-modification of bacteria.
FIG. 5 is a graph showing AC impedance curves of electrodes prepared in this example and electrodes of comparative example, and it can be seen that the internal resistance of the electrode material is significantly reduced after self-modification by bacteria and the electric double layer effect is promoted. According to the constant-current charging and discharging curve of the electrode prepared by the embodiment under different current densities, the specific capacitance of the composite electrode is up to 256F/g under the current density of 0.5A/g through calculation; when the current density is increased to 20A/g, the capacitance value is 206F/g, the capacitance attenuation is small, 80% of capacitance can be reserved, and excellent rate performance is shown.
The cyclic voltammetry curve is measured under a three-electrode system, and the result shows that the self-modified and derived porous carbon supercapacitor electrode material of the bacteria has good cyclic stability, and the specific capacitance is still kept above 95% after 3000 cycles under the current density of 20A/g.
Example 2
(1) The seed liquid of Rhodococcus opacus PD630 was obtained by culturing according to the steps (1) and (2) in example 1.
(2) Centrifuging the obtained Rhodococcus opacus PD630 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Rhodococcus opacus PD630 thallus into a low-nitrogen glucose culture medium according to the inoculation amount of 10%, culturing at the temperature of 30 ℃ and natural pH for 48h, and performing centrifugal separation at 8000rpm to obtain bacterial thallus; the low-nitrogen glucose culture medium comprises the following components in parts by weight: 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) Putting the Rhodococcus opacus PD630 thallus obtained in the last step into a vacuum freeze dryer to constant weight to obtain dry thallus.
(5) And (2) placing the dried thalli in a tubular furnace, standing at 700 ℃ for 3h at a heating speed of 5 ℃/min under the nitrogen atmosphere, naturally cooling to room temperature, washing the obtained product with dilute hydrochloric acid and deionized water until the pH value of the solution is 7, and drying the obtained precipitate at 80 ℃ for 12h to obtain the bacterial self-modifying derivative porous carbon.
The specific surface area of the porous carbon prepared by the practice of this example was 1085m2/g。
The electrochemical properties were measured in the same manner as in example 1. The specific capacitance of the porous carbon electrode is up to 228F/g under the condition that the current density is 0.5A/g; when the current density is increased to 20A/g, the capacitance value is 196F/g, the capacitance attenuation is small, 85% of capacitance can be reserved, and excellent rate performance is shown.
Example 3
(1) The seed liquid of Rhodococcus opacus PD630 was obtained by culturing according to the steps (1) and (2) in example 1.
(2) Centrifuging the obtained Rhodococcus opacus PD630 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Rhodococcus opacus PD630 thallus into a low-nitrogen glucose culture medium according to the inoculation amount of 5%, culturing at the temperature of 30 ℃ and natural pH for 24h, and performing centrifugal separation at 8000rpm to obtain bacterial thallus; the low-nitrogen glucose culture medium comprises the following components in parts by weight: 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；K2HPO4 2.14g/L，KH2PO4 1.33g/L。
(4) Putting the Rhodococcus opacus PD630 thallus obtained in the last step into a vacuum freeze dryer to constant weight to obtain dry thallus.
(5) And (2) placing the dried thalli in a tubular furnace, standing at 800 ℃ for 1h at a heating rate of 5 ℃/min under the nitrogen atmosphere, naturally cooling to room temperature, washing the obtained product with dilute hydrochloric acid and deionized water until the pH value of the solution is 7, and drying the obtained precipitate at 80 ℃ for 12h to obtain the bacterial self-modifying derivative porous carbon.
The specific surface area of the porous carbon obtained by the practice of this example was 1133m2/g。
The electrochemical properties were measured in the same manner as in example 1. The specific capacitance of the porous carbon electrode is up to 246F/g under the condition that the current density is 0.5A/g; when the current density is increased to 20A/g, the capacitance value is 204F/g, the capacitance attenuation is small, 83% of capacitance can be reserved, and excellent rate performance is shown.
Comparative example 1
The preparation method of the porous carbon related to the comparative example adopts a normal nitrogen content culture medium, and the bacteria do not accumulate PHA under the condition, and the specific steps are as follows:
(1) inoculating Rhodococcus opacus PD630 bacteria stored on an LB inclined plane into an LB liquid culture medium, and culturing at 30 ℃ for 18h to obtain a seed solution of the Rhodococcus opacus PD 630; wherein the LB liquid culture medium comprises the following components in percentage by weight: 10g of peptone, 5g of yeast powder, 10g of sodium chloride and 1L of distilled water; the LB inclined plane is formed by adding 15g/L agar on the basis of the formula;
(2) centrifuging the Rhodococcus opacus PD630 seed solution obtained in the last step for 5 minutes at 8000rpm, discarding the supernatant, and collecting the thallus;
(3) inoculating the collected Rhodococcus opacus PD630 into a glucose culture medium with normal nitrogen content according to the inoculation amount of 2%, culturing at the temperature of 30 ℃ and natural pH for 24h, and performing centrifugal separation at 8000rpm to obtain bacterial thalli; wherein the normal nitrogen content glucose culture medium comprises the following components in percentage by weight: 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；K2HPO4 2.14g/L，KH2PO41.33g/L。
(4) Putting the Rhodococcus opacus PD630 thallus obtained in the last step into a vacuum freeze dryer to constant weight to obtain dry thallus.
(5) And (2) placing the dried thalli in a tubular furnace, standing at 900 ℃ for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, naturally cooling to room temperature, washing the obtained product with dilute hydrochloric acid and deionized water until the pH value of the solution is 7, and drying the obtained precipitate at 80 ℃ for 12h to obtain the unmodified bacteria-derived porous carbon.
The porous carbon prepared by this comparative example had a specific surface area of 162m2Is much lower than that of the bacterial self-modified derivative porous carbon (-1199 m)2In terms of/g). FIG. 2 is an SEM image of the unmodified cell-derived porous carbon prepared in the comparative example, and it can be seen that the material surface has few smooth pores.
The electrochemical properties were measured in the same manner as in example 1. At a current density of 0.5A/g, the specific capacitance was 46F/g, which was lower than that of the examples (241F/g). The ac impedance curve shown in fig. 5 also indicates that the comparative example electrode material has a greater internal resistance relative to the example. The results show that the specific surface area, the pore channel structure and the electrochemical properties of the derived porous carbon can be obviously improved by the bacterial self-modification effect realized by regulating and controlling the nitrogen source.
Comparative example 2
(1) The seed liquid of Rhodococcus opacus PD630 was obtained by culturing according to the steps (1) and (2) in example 1.
(2) Centrifuging the obtained Rhodococcus opacus PD630 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) collecting the collected RhodoInoculating coccus opacus PD630 thallus into a low-nitrogen glucose culture medium according to the inoculation amount of 10%, culturing at the temperature of 30 ℃ and natural pH for 96h, and performing centrifugal separation at 8000rpm to obtain bacterial thallus; the low-nitrogen glucose culture medium comprises the following components in parts by weight: 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；K2HPO4 2.14g/L，KH2PO4 1.33g/L。
(4) Putting the Rhodococcus opacus PD630 thallus obtained in the last step into a vacuum freeze dryer to constant weight to obtain dry thallus.
(5) And (2) placing the dried thalli in a tubular furnace, standing at 900 ℃ for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, naturally cooling to room temperature, washing the obtained product with dilute hydrochloric acid and deionized water until the pH value of the solution is 7, and drying the obtained precipitate at 80 ℃ for 12h to obtain the bacterial self-modifying derivative porous carbon.
The porous carbon prepared by this comparative example 2 had a specific surface area of 731m2G, much lower than in the example (. about.1199 m)2In terms of/g). The electrochemical properties were measured in the same manner as in example 1. At a current density of 0.5A/g, the specific capacitance was 153F/g lower than that of the examples (241F/g). The results show that the PHA accumulated in the cells is consumed by bacteria to obviously reduce the performance of the derived carbon, and the modification effect of the PHA accumulated by the bacteria is proved to improve the specific surface area, the pore structure and the electrochemical properties of the derived porous carbon.
Claims (6)
1. A preparation method of a porous carbon material prepared by utilizing rhodococcus turbinatus self-modification is characterized by comprising the following steps:
(1) inoculating the rhodococcus turbinatus in a low-nitrogen sterile culture medium, and after culturing, carrying out solid-liquid separation and drying to obtain a product; the culture condition of the rhodococcus turbinatus is that the inoculum size is 2-10%, the temperature is 25-40 ℃, the natural pH condition is adopted, and the culture time is 18-48 h; the obtained product is rhodococcus turbinatus with PHA accumulated in cells,
(2) and (2) putting the product obtained in the step (1) into an inert atmosphere for carbonization treatment, and purifying the obtained carbonized product to obtain the porous carbon material.
2. The method for preparing a porous carbon material by using self-modification of rhodococcus turbinatus according to claim 1, wherein: the Rhodococcus turbidivorus is Rhodococcus opacus PD630 with the preservation number of DSMZ No. 44193.
3. The method for preparing a porous carbon material by using self-modification of rhodococcus turbinatus according to claim 1, wherein the porous carbon material is prepared by: the specific surface area of the porous carbon material is 1085-1379 m2/g。
4. The method for preparing a porous carbon material by using self-modification of rhodococcus turbinatus according to claim 1, wherein the porous carbon material is prepared by: in the step (1), the low-nitrogen sterile culture medium is a sterile culture medium which takes glucose as a unique carbon source and has the component of 5g/L, NH of glucose4Cl0.5-1.2g/L、MgSO4·7H2O 1.0g/L、CaCl2·2H2O0.015 g/L、CoCl2·6H2O 0.050mg/L、CuCl2·2H2O0.0050 mg/L、EDTA0.25mg/L、FeSO4·7H2O 0.50mg/L、H3BO30.015mg/L、MnSO4·H2O 0.020mg/L、NiC12·6H2O 0.010mg/L、ZnSO4·7H2O 0.40mg/L、FeNa-EDTA5.0g/L、NaMoO4·H2O 2.0mg/L；K2HPO4 2.14g/L，KH2PO4 1.33g/L。
5. The method for preparing a porous carbon material by using self-modification of rhodococcus turbinatus according to claim 1, wherein the porous carbon material is prepared by: in the step (1), the solid-liquid separation mode is centrifugal separation, and the rotating speed of the centrifugal separation is 6000-8000 rpm;
in the step (1), the drying mode is that the mixture is frozen and dried in vacuum to constant weight;
in the step (2), the temperature of the carbonization treatment is 700-;
in the step (2), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
6. The application of the porous carbon material prepared by the self-modification of the rhodococcus turbinatus according to the preparation method of any one of claims 1 to 5 is characterized in that: applying the porous carbon material to a supercapacitor.
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