CN114506837A - Method for regulating and controlling pore canal orientation of carbon aerogel, carbon aerogel and application - Google Patents
Method for regulating and controlling pore canal orientation of carbon aerogel, carbon aerogel and application Download PDFInfo
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- CN114506837A CN114506837A CN202210136447.6A CN202210136447A CN114506837A CN 114506837 A CN114506837 A CN 114506837A CN 202210136447 A CN202210136447 A CN 202210136447A CN 114506837 A CN114506837 A CN 114506837A
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- 238000010000 carbonizing Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 241000228212 Aspergillus Species 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
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- 239000003463 adsorbent Substances 0.000 claims 1
- 230000001143 conditioned effect Effects 0.000 claims 1
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- 150000001875 compounds Chemical class 0.000 abstract description 5
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- 239000007788 liquid Substances 0.000 description 6
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- 238000000967 suction filtration Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 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 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
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Images
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
Abstract
The invention provides a method for regulating and controlling pore canal orientation of carbon aerogel, the carbon aerogel and application. Adding m-phenylenediamine dispersed in an aqueous solution into a filamentous fungus mixed solution by taking filamentous fungi as an assembly framework, oscillating and stirring, adding ammonium persulfate to polymerize the m-phenylenediamine to obtain a mycelium-poly (m-phenylenediamine) compound, then freezing and molding in a cold field, then performing freeze drying and demolding, and finally performing high-temperature pyrolysis in an inert atmosphere to obtain the carbon aerogel. The invention reduces the mass transfer resistance of the solution in the material by controlling the orientation of the carbon aerogel channel, and can obviously enhance the electric adsorption capacity of the carbon aerogel.
Description
Technical Field
The invention belongs to the technical field of inorganic nano porous materials and preparation thereof, and relates to a method for regulating and controlling pore canal orientation of carbon aerogel, the carbon aerogel and application.
Background
The Capacitive Deionization (CDI) technology has the advantages of no secondary pollution, simplicity and convenience in operation and the like, is widely applied to the fields of seawater desalination, brackish water purification and the like, and has great application prospects.
Electrode materials are critical in determining CDI performance. Carbon materials, metal oxides, Ag/Bi, Mxene and the like are widely used in CDI electrodes. However, the conventional electrode preparation method is mainly a coating method, the material usage amount is small, and the binder seals the pore diameter of the material to reduce the active area, thereby weakening the performance of the electrode material. The preparation of the molded body electrode from the powder material, avoiding the use of a binder and greatly increasing the material consumption, has proved to be a feasible method for improving the CDI treatment efficiency.
However, in general, the channels of the shaped body electrode are short-range and disordered and have closed pores, the reaction is more likely to occur on the outer surface or easily accessible mesopores, and most of the material surface cannot function, thus generating waste. Particularly, when the method is applied to the field of CDI, an electric double layer can be rapidly formed on the surface of a material, electrostatic repulsion can hinder the migration of charged substances from a bulk solution to the surface of an electrode, and irregular pore channels can prolong the fluid passing time and slow the adsorption balance, thereby affecting the adsorption rate. Thus, the irregularities of the pores of the shaped body greatly limit its application.
The carbon aerogel molded body electrode with regular pore channel orientation is constructed by taking hypha and aromatic amine monomers as raw materials through accurately regulating and controlling a temperature field, and the influence of the pore channel orientation of the molded body electrode on the CDI performance is investigated.
Meanwhile, based on the characteristics of the carbon aerogel with the regular pore canal orientation prepared by the method, the carbon aerogel can be expanded and applied to wider technical fields, such as the field of energy battery cathode materials or adsorption materials.
Disclosure of Invention
The invention aims to provide a carbon aerogel with controllable pore channel orientation, and the directions of internal pore channels of the material are consistent. And the regular pore channels with the same direction can shorten the fluid passing time and accelerate the adsorption balance, greatly improves the adsorption performance of the material, and can obviously improve the CDI treatment efficiency when being particularly applied to the CDI field.
The carbon aerogel is obtained by reacting filamentous fungi with aromatic amine monomers and an oxidant to obtain a hypha @ polyaromatic amine compound, and then carrying out cold field treatment, freeze drying and high-temperature carbonization on the hypha @ polyaromatic amine compound; the cold field treatment refers to cooling treatment of one flat surface or two opposite flat surfaces on the material three-dimensional shape; preferably, the cold source is directly contacted with the flat surface of the material in the three-dimensional shape, or is contacted with the flat surface through a heat-conducting sheet; when the material is in a three-dimensional shape of a cylinder, the two bottom surfaces of the cylinder or the whole side surface of the cylinder is subjected to cooling treatment.
The pore diameter range of the carbon aerogel material is 5um-200 um.
The second purpose of the invention is to provide a preparation method of the carbon aerogel. The preparation method is simple, simple and convenient to operate, low in cost and convenient for large-scale production, and specifically comprises the following steps:
a method for regulating and controlling the pore channel orientation of a carbon aerogel, comprising the following steps:
1) carrying out polymerization reaction on the filamentous hypha, the aromatic amine monomer and the oxidant to obtain a hypha @ polyaromatic amine compound, and forming in a three-dimensional mold;
2) uniformly contacting the hypha in a three-dimensional shape formed by a mold with a cold source for treatment, or contacting the hypha in a cylindrical shape with one surface or two opposite surfaces of a polyaromatic amine compound, or contacting the hypha in a cylindrical shape with the cold source for treatment through a heat-conducting sheet;
3) step 2), freeze-drying and dehydrating the mycelium @ polyaromatic amine compound obtained after treatment to obtain mycelium @ polyaromatic amine aerogel;
4) and carbonizing the mycelium @ polyaromatic amine aerogel at high temperature in an inert atmosphere to obtain the carbon aerogel.
Further, the temperature of the cold source in the step 2) is-40 to-5 ℃, preferably-25 to-10 ℃, and further preferably-20 to-15 ℃.
The cold source temperature is too high, the freezing speed is too slow, and slurry is caused to sink to the bottom and the density is not uniform; the freezing temperature is too low, the freezing rate is too high, ice crystals can not grow up to form a compact layer, and the pores of the aerogel are too small.
Further, the cold source treatment time of the step 2) is 5 to 20 hours, preferably 2 to 12 hours, and further preferably 4 to 6 hours.
The mycelium @ polyaromatic amine compound obtained in the step 1) in the method is preferably molded in a mold to form a three-dimensional material with a flat surface, so that the three-dimensional material is in contact with a cold source, and the reaction efficiency is improved.
The invention can select the cold source to contact with one surface or two opposite surfaces of the three-dimensional shape of the material in the direction. For example, when the molding material is a cube, only one of the two planes may be selected, or two opposite planes may be selected to contact the heat sink. When the material is in a three-dimensional shape of a cylinder, the two bottom surfaces of the cylinder or the whole side surface of the cylinder is subjected to cooling treatment. The contact means may also be mediated by a thermally conductive foil.
The three-dimensional shape includes: cubes, cylinders, cones, polyhedrons, triangular pyramids, and the like.
The heat conducting sheet is prepared from various heat conducting metals or other heat conducting materials.
In the above-mentioned method, the first step,
the filamentous fungi comprise one or more of aspergillus aculeatus, aspergillus niger, aspergillus flavus, aspergillus rhizogenes and penicillium.
The aromatic amine monomer comprises one or more of aniline, pyrrole and m-phenylenediamine.
The oxidant comprises a persulfate, preferably sodium persulfate or ammonium persulfate.
The mass ratio of the aromatic amine monomer to the dry pure hyphae is 2:1-1:10, preferably 1:1-1: 5, more preferably 1: 2.
and scattering the dried pure hyphae by using cultured filamentous fungi, performing suction filtration to form a cake, freezing by using liquid nitrogen, and freeze-drying for 24 hours until the pure hyphae are completely dehydrated to obtain the mycelium.
The molar ratio of the oxidant to the aromatic amine monomer is 1:0.5-1:3, preferably 1:1-1:1.5, more preferably 1: 1.2.
the concentration of the dispersion of the hypha @ polyaromatic amine complex obtained in step 1) is 5-50g/L, preferably 20-40g/L, and more preferably 25 g/L.
The freeze drying temperature in the step 3) is-20 ℃ to-90 ℃, preferably-60 ℃ to-90 ℃, and further preferably-80 ℃; the time is 12 to 48 hours, preferably 12 to 36 hours, and more preferably 24 hours.
The carbonization temperature in the step 4) is 400-1100 ℃, the carbonization time is 1-10h, the preferable temperature is 600-800 ℃, and the preferable time is 2-4 h.
The inert atmosphere in the step 4) is nitrogen or argon.
The method for regulating and controlling the pore canal orientation of the carbon aerogel is optimized in further detail as follows:
the method comprises the following steps: culturing filamentous fungi by liquid phase method; the culture medium is prepared by dissolving 10-50 g of potato glucose broth powder in 0.5-2L of deionized water, and adding 0.5-2 g of potassium dihydrogen phosphate and 0.2-1 g of magnesium sulfate; the temperature for culturing the filamentous fungi is 5-37 ℃, and the culturing is carried out in a shaking environment, wherein the shaking speed is not more than 300rpm, and preferably 100-200 rpm; the culture time is 6-120h, preferably 72-96 h.
Step two: stirring and dispersing the cultured filamentous fungi by using an electric stirrer, repeatedly washing by using deionized water, performing suction filtration, and freeze-drying for later use;
step three: weighing a certain amount of hypha, adding the hypha into deionized water to obtain a hypha dispersion liquid, adding an aromatic amine monomer, adding a certain amount of oxidant after a precursor is dissolved to polymerize the monomer, repeatedly washing with deionized water to obtain a hypha @ polyaromatic amine compound, and storing at normal temperature;
step four: weighing a certain amount of hypha @ polyaromatic amine compound, adding a certain volume of deionized water to obtain a hypha @ polyaromatic amine dispersion liquid, closing a container, and performing ultrasonic dispersion; the concentration of the dispersion is 5-50 g/L;
step five: contacting the bottom plane of the container with a cold source for treatment; the bottom of the container is a heat-conducting sheet, and the rest surfaces are made of polytetrafluoroethylene (which can preserve heat);
step six: freeze drying until completely dehydrating to obtain mycelium @ polyaromatic amine aerogel;
step seven: and carbonizing the mycelium @ polyaromatic amine aerogel at high temperature in an inert atmosphere to obtain the carbon aerogel.
The third purpose of the invention is to provide the carbon aerogel or the application of the carbon aerogel regulated and obtained by the method. The method is particularly used for preparing energy batteries (air electrode materials), sensors (pressure sensors) or adsorbing materials, and further used for preparing CDI electrode materials.
When used for preparing the adsorbing material, the method can be used for adsorbing: gases, heavy metals or organic matter; further used for preparing CDI electrode material.
The invention has the beneficial effects that:
(1) the invention uses the filamentous fungi as the raw material, and has the advantages of environmental protection and large surface area;
(2) the method regulates and controls the pore canal orientation of the carbon aerogel by a specific cold conduction means for the first time, is green and environment-friendly, is quick to mold, is simple to demold, is beneficial to large-scale production, and can be molded in one step compared with a method for preparing a molded body electrode by using a powder material in the prior art when being particularly applied to a CDI electrode material, so that the operation is simplified, and the cost is saved.
(3) The pore channel orientation-controllable carbon aerogel prepared by the method has excellent mechanical properties and has wide application prospects in the fields of energy batteries, sensors, adsorption and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a tunnel disordered hypha-m-phenylenediamine carbon aerogel in example 3;
FIG. 2 is a scanning electron microscope image of a vertically oriented hypha-m-phenylenediamine carbon aerogel in the channel of example 4;
FIG. 3 is a scanning electron micrograph of horizontally oriented hypha-m-phenylenediamine carbon aerogel in the pore canals of example 5;
FIG. 4 is a graph of the electro-adsorption performance of various materials measured in example 6.
The invention is further illustrated below with reference to specific examples. These embodiments are merely illustrative and are not intended to limit the scope of the present invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
Liquid phase method is adopted to culture and produce Aspergillus niger in large scale. A potato glucose broth culture medium is adopted, 25g of potato glucose broth, 0.5g of anhydrous magnesium sulfate and 1g of dipotassium phosphate are added into 1 liter of deionized water, the mixture is sterilized for 15 minutes at 121 ℃, bacterial spots in a flat culture medium are inoculated into a sterilized liquid culture medium, and the liquid culture medium is placed in a shaking table for culture. The temperature was controlled at 30 ℃ and the shaking rate at 150 rpm. The growth of Aspergillus niger reached its peak value in 3 days.
Pouring the cultured filamentous fungi into a 1000mL blue-mouth bottle, stirring for 5h at 1500rpm of an electric stirrer, and scattering for 3min by using a juicer. And (3) carrying out suction filtration and separation on the dispersion liquid by using a G-2 sand core funnel, respectively rinsing with deionized water and absolute ethyl alcohol, carrying out suction filtration to obtain cakes, placing the cakes into a liquid nitrogen operation basin, adding liquid nitrogen, and quickly freezing. And after freezing, transferring the strain to a freeze dryer, and freeze-drying for 24h until the strain is completely dehydrated to obtain the dried pure hyphae.
Example 2
2g of the dried pure hyphae obtained in example 1 were added to 200mL of deionized water and stirred to disperse, and then 1g of m-phenylenediamine was added and stirred at 500rpm for 1 hour. Weighing 2.1g of ammonium persulfate to dissolve in 30ml of deionized water, slowly dripping into the hypha-m-phenylenediamine suspension, continuously stirring for 2 hours to obtain hypha-poly (m-phenylenediamine) suspension, and performing suction filtration to obtain a cake to obtain the compact hypha-poly (m-phenylenediamine) composite material.
Example 3
Putting the hypha-poly (m-phenylenediamine) composite material obtained in the example 2 into an all-aluminum cylindrical mold (the side wall and the lower bottom of the mold and the upper cover are all made of all-aluminum materials), adding 30mL of deionized water, stirring for 1h, the concentration is 25g/L, performing ultrasonic dispersion for 30min, then transferring the mold into a refrigerator at-20 ℃ to freeze for 4h, performing cold field dispersion in the refrigerator, ensuring the temperature to be uniform, transferring the frozen aerogel into a freeze dryer, performing freeze drying at-80 ℃ for 24h until the aerogel is completely dehydrated, then putting the dehydrated aerogel into a tubular furnace, raising the temperature rate at 2 ℃/min to 800 ℃ to perform pyrolysis for 2h, and obtaining hypha-poly (m-phenylenediamine) carbon aerogel with disordered internal pore channels, wherein a scanning electron microscope picture of the gel is shown in figure 1.
Example 4
Placing the hypha-poly (m-phenylenediamine) compound obtained in the example 2 into a cylindrical mold (the upper bottom of the mold is covered by a foam plate) with polytetrafluoroethylene on the side wall, adding 30mL of deionized water, stirring for 1h, ultrasonically dispersing for 30min, transferring the mold onto a freezing platform, transferring a cold field from the freezing platform (the temperature is minus 20 ℃) to the copper bottom, freezing for 4h from bottom to top, transferring the frozen hypha-poly (m-phenylenediamine) compound into a freeze dryer, freeze-drying for 24h at minus 80 ℃ until complete dehydration is achieved, placing the dehydrated aerogel into a tubular furnace, increasing the temperature rise rate at 2 ℃/min to 800 ℃ for pyrolysis for 2h, obtaining the hypha-poly (m-phenylenediamine) carbon aerogel with internal pore channels from bottom to top, and obtaining a scanning electron microscope picture shown in figure 2.
Example 5
Putting the mycelium-poly (m-phenylenediamine) compound obtained in the example 2 into a cylindrical mold, adding 30mL of deionized water, stirring for 1h, ultrasonically dispersing for 30min, wherein the side wall of the mold is a copper wall, sealing the upper bottom surface and the lower bottom surface of the mold by using heat-insulating material polytetrafluoroethylene, transferring the mold into a refrigerator, freezing for 4h (the side surface takes the low temperature in the refrigerator as a cold source, and a cold field can only conduct from the copper wall on the periphery of the container to the inside of the container, namely a low-temperature field provided by the refrigerator), transferring the frozen mycelium-poly (m-phenylenediamine) compound into a freeze drier at the temperature of-20 ℃ due to the cold insulation of the upper and lower bottoms, conducting from the copper wall to the inside, freezing and drying for 24h at the temperature of-80 ℃ until the mycelium is completely dehydrated, putting the dehydrated mycelium into a tubular furnace, and raising the temperature of aerogel at the rate of 2 ℃/min to 800 ℃ for pyrolysis for 2h to obtain aerogel-poly (m-phenylenediamine) carbon aerogel (with the inner pore channel being vertical to the side surface of the cylindrical mold and in the horizontal direction (and the inner pore All the way directions point to the center of the cylinder), and the scanning electron microscope image is shown in figure 3.
Example 6
The materials obtained in examples 3, 4 and 5 were placed in a penetration type electric adsorption apparatus, and charged at a voltage of 1.2V, 500mg/L of a chloride ion solution was injected into the apparatus at a rate of 10mL/min to adsorb for 2 hours, and 7 samples were taken in total to measure the chloride ion content. The results as shown in FIG. 4 were obtained. It can be seen from the figure that the longitudinal pore carbon aerogel (example 4) reaches the highest adsorption saturation and has the highest adsorption capacity, the horizontal pore carbon aerogel (example 5) and the disordered pore carbon aerogel (example 3) reach the adsorption saturation at a similar rate, and the non-directional pore carbon aerogel has the lowest adsorption capacity.
Claims (10)
1. A carbon aerogel characterized by having uniform internal pore directions.
2. The carbon aerogel according to claim 1, wherein hypha @ polyaromatic amine complex obtained by reacting filamentous fungi with aromatic amine monomers and an oxidizing agent is obtained by cold field treatment, freeze drying and high temperature carbonization; the cold field treatment refers to cooling treatment of one flat surface or two opposite flat surfaces on the material three-dimensional shape; preferably, the cold source is directly contacted with the flat surface of the material in the three-dimensional shape, or is contacted with the flat surface through a heat-conducting sheet; when the material is in a three-dimensional shape of a cylinder, the two bottom surfaces of the cylinder or the whole side surface of the cylinder is subjected to cooling treatment.
3. The method of regulating the pore orientation of a carbon aerogel according to claim 2, comprising the steps of:
1) carrying out polymerization reaction on the filamentous hypha, the aromatic amine monomer and the oxidant to obtain a hypha @ polyaromatic amine compound, and forming in a three-dimensional mold;
2) uniformly contacting the hypha in a three-dimensional shape formed by a mold with a cold source for treatment, or contacting the hypha in a cylindrical shape with one surface or two opposite surfaces of a polyaromatic amine compound, or contacting the hypha in a cylindrical shape with the cold source for treatment through a heat-conducting sheet;
3) step 2), freeze-drying and dehydrating the mycelium @ polyaromatic amine compound obtained after treatment to obtain mycelium @ polyaromatic amine aerogel;
4) and carbonizing the mycelium @ polyaromatic amine aerogel at high temperature in an inert atmosphere to obtain the carbon aerogel.
4. The method of claim 3,
the temperature of the cold source in the step 2) is-40 to-5 ℃, preferably-25 to-10 ℃, and further preferably-20 to-15 ℃.
5. The method of claim 3,
the cold source treatment time of the step 2) is 5-20h, preferably 2-12h, and further preferably 4-6 h.
6. The method of claim 3,
the filamentous fungi comprise one or more of aspergillus aculeatus, aspergillus niger, aspergillus flavus, aspergillus rhizogenes and penicillium; the aromatic amine monomer comprises one or more of aniline, pyrrole and m-phenylenediamine; the oxidant comprises a persulfate, preferably sodium persulfate or ammonium persulfate.
7. The method according to claim 3, wherein the mass ratio of aromatic amine monomer to dry pure hyphae is 2:1-1:10, preferably 1:1-1: 5, more preferably 1: 2;
the molar ratio of the oxidant to the aromatic amine monomer is 1:0.5-1:3, preferably 1:1-1:1.5, more preferably 1: 1.2.
8. the method according to claim 3, wherein the concentration of the dispersion of mycelium @ polyaromatic amine complex obtained in step 1) is 5-50g/L, preferably 20-40g/L, more preferably 25 g/L.
9. A method according to claim 3, characterized in that the freeze-drying temperature in step 3) is-20 ℃ to-90 ℃, preferably-60 ℃ to-90 ℃, more preferably-80 ℃; the time is 12-48h, preferably 12-36h, and further preferably 24 h;
the carbonization temperature in the step 4) is 400-1100 ℃, the carbonization time is 1-10h, the preferable temperature is 600-800 ℃, the preferable time is 2-4h, and the inert atmosphere is nitrogen or argon.
10. Use of the carbon aerogel of claim 1 or 2, or the carbon aerogel conditioned by the method of any of claims 3-9, for the preparation of an energy cell negative electrode or adsorbent material, further for the preparation of a CDI electrode material.
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