CN103449406A - Powdery carbon aerogel, as well as preparation method and application thereof - Google Patents
Powdery carbon aerogel, as well as preparation method and application thereof Download PDFInfo
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- CN103449406A CN103449406A CN2013103906437A CN201310390643A CN103449406A CN 103449406 A CN103449406 A CN 103449406A CN 2013103906437 A CN2013103906437 A CN 2013103906437A CN 201310390643 A CN201310390643 A CN 201310390643A CN 103449406 A CN103449406 A CN 103449406A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000004966 Carbon aerogel Substances 0.000 title abstract description 9
- 239000004964 aerogel Substances 0.000 claims abstract description 157
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 239000003814 drug Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 110
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 70
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- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 23
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- 235000019394 potassium persulphate Nutrition 0.000 claims description 21
- 230000008961 swelling Effects 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
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- 239000013543 active substance Substances 0.000 claims description 17
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- -1 polyethylene Polymers 0.000 claims description 10
- 239000002077 nanosphere Substances 0.000 claims description 9
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- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
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- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 32
- 238000001179 sorption measurement Methods 0.000 description 32
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- 241000628997 Flos Species 0.000 description 30
- 238000010992 reflux Methods 0.000 description 30
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 20
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- 238000010907 mechanical stirring Methods 0.000 description 16
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- 238000001485 positron annihilation lifetime spectroscopy Methods 0.000 description 15
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- 239000011148 porous material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 description 2
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- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Carbon And Carbon Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention belongs to the technical field of an aerogel material and discloses a powdery carbon aerogel, as well as a preparation method and an application thereof. The powdery carbon aerogel is formed by carbon nanometer ball building units with a grain size of 20-300 nm by cross-linking and stacking; lots of micropores are formed on the surface of the carbon nanometer balls, and the specific surface area is 294-2472 m<2>/g. The powdery carbon aerogel disclosed by the invention is micron-level powder, can be directly used without being ball-milled in lots of application fields, and contributes to simplification of an application technique. The powdery carbon aerogel disclosed by the invention has a high specific surface area which is as high as 2472m<2>/g at most, and has wide potential application in preparation of electrode materials, medicine release control materials and adsorbing materials. Moreover, the building unit of the powdery carbon aerogel has good sphericity degree and grain size uniformity, and is benefit for precise building of a nanometer structure. The preparation method of the powdery carbon aerogel is simple, realizes moderate and easily controlled reaction condition, and is beneficial to industrialization amplification.
Description
Technical field
The invention belongs to the aerogel material technical field, particularly a kind of Powdered charcoal-aero gel and its preparation method and application.
Background technology
Carbon aerogel material, once appearance, causes countries in the world research worker's great interest.In recent years, people have carried out a large amount of research work at aspects such as cheap raw material exploitation, work simplification (especially drying process), structure control, performance characterization and application and developments.But even to this day, no matter aerogel material is aspect fundamental research, or aspect production application, all still in the exploratory stage.
The synthetic sol gel reaction based on phenolic aldehyde solution usually of current this class material.There is various problems in this preparation method: (1) obtains the bakelite resin nano particulate units by colloidal sol reaction, and and then utilizing gelation reaction that these unit are cross-linked to form to the nanocarbon particle unit that the three-dimensional manometer network forms after charing again is all atresia atresia or accurate.(2) the sol gel reaction normally completes in standing encloses container, causes the heat in polymerization process to be difficult to rapid derivation, the implode that can cause danger in the technique amplification process.(3) the charcoal-aero gel presoma mechanical strength obtained after most of sol gel reaction is low, therefore can't bear the strong kapillary convergent force produced in the solvent seasoning process under normal pressure, usually need the technology such as adopting process is loaded down with trivial details, cost is expensive supercritical drying or lyophilize to remove solvent.(4) aerogel material that reaction obtains through sol gel generally is block, can't meet the diversified demand of application.For example, charcoal-aero gel, through being often used as electrode material for super capacitor, at this moment must become micron powder (～10 μ m) to the Monolithic aerogel ball milling, not only wastes time and energy, also expensive.
Summary of the invention
For the shortcoming and deficiency that overcome above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of Powdered charcoal-aero gel.
Another purpose of the present invention is to provide a kind of preparation method of above-mentioned Powdered charcoal-aero gel.
Still a further object of the present invention is to provide the application of above-mentioned Powdered charcoal-aero gel in preparing electrode materials, drug release material and sorbing material.
Purpose of the present invention realizes by following proposal:
Crosslinked stacking the forming of the carbon nanospheres construction unit that a kind of Powdered charcoal-aero gel is 20～300nm by particle diameter, there are a large amount of micropores on the carbon nanospheres surface, and its specific surface area is 294～2472m
2/ g.
Crosslinked and a large amount of mesopores of stacking formation and macropore between the carbon nanospheres ball of above-mentioned Powdered charcoal-aero gel, mutually run through connection between each duct, formation has stratification nanometer network pore passage structure unique, that three-dimensional is connected, between each level nano pore, has synergistic effect.
The preparation method of above-mentioned Powdered charcoal-aero gel comprises following concrete steps:
(1) preparation of polystyrene-divinylbenzene (PSDVB) nanometer ball: tensio-active agent is added to the water, is stirred to fully and dissolves, add St monomer and Vinylstyrene (DVB), after being uniformly dispersed, add initiator, the heated polymerizable reaction; Alcohol precipitation, after centrifugal, washing, drying, obtain the PSDVB nanometer ball;
(2) step (1) gained PSDVB nanometer ball is added in anhydrous tetracol phenixin, stir swelling; Add aluminum trichloride (anhydrous), the stirring heating crosslinking reaction; Add acetone/hydrochloric acid/water mixed solvent termination reaction, after filtration, washing, drying, obtain organic aerogel; Under the noble gas atmosphere, high temperature carbonization, obtain Powdered charcoal-aero gel.
The consumption of tensio-active agent described in step (1) is that every 160mL water is used 0.9～18.3g tensio-active agent.
(micro-) emulsion polymerization is the gentle controlled type of polymerization of environmental friendliness with water as solvent.Under the effect of emulsifying agent and by means of mechanical stirring, monomer is dispersed into milk sap in water, and the free radical generated in water medium enters in micella or emulsion particle and causes wherein monomer and carry out polymerization.Adopt the emulsifying agent of suitable kind and concentration, can form the micella of stable uniform, thereby synthesize the product of homogeneous.In preparation process of the present invention, adopt the method for (micro-) letex polymerization to be conducive to synthesize the dispersed nano ball of uniform particle diameter good sphericity, make the aerogel of follow-up preparation have the uniform carbon nanospheres construction unit of pattern.Simultaneously add a certain amount of DVB in the process of (micro-) letex polymerization, thereby can make the PSDVB nanometer ball of preparation there is certain precrosslink degree, there is certain physical strength, can avoid after form the process of aerogel in the subsiding of structure.And by regulating kind and the concentration of emulsifying agent, thereby the size of controlled glue bundle is controlled the size of PSDVB nanometer ball and further carbon nanospheres.Change the condition of letex polymerization, can make the nanometer ball size distribution obtained between 20～300nm, make the construction unit variation of charcoal-aero gel.
Preferably, the consumption of described tensio-active agent is that every 160mL water is used the 18.3g tensio-active agent.
Tensio-active agent described in step (1) refers at least one in polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (P123), sodium lauryl sulphate (SDS) and Trimethyllaurylammonium bromide (DTAB).
When described tensio-active agent is SDS, also need to add cosurfactant, as ethanol or Pentyl alcohol.
The amount of assistant for emulsifying agent used is that every 100ml solvent adds the 3g assistant for emulsifying agent.
Preferably, described tensio-active agent refers to P123.
Initiator described in step (1) refers to Potassium Persulphate (KPS) or Diisopropyl azodicarboxylate (AIBN).
Preferably, described initiator refers to KPS.
St:DVB used in step (1): initiator: the mass ratio of tensio-active agent is 4:(0.2～4): (0.04～0.08): (0.16～18.3).
Heated polymerizable reaction described in step (1) refers at 70～80 ℃ of reaction 3～24h.
Alcohol precipitation described in step (1) refers to add methyl alcohol, makes product form throw out precipitate and separate.
The volume ratio of methyl alcohol used and emulsion is 160:500.
Drying described in step (1) refers to dry 12～24h under 50 ℃.
In step (2), the mass ratio of PSDVB nanometer ball used and aluminum trichloride (anhydrous) is 0.5:(0.7～2.8).
In step (2), the amount of anhydrous tetracol phenixin used is that every 1g PSDVB nanometer ball is used the anhydrous tetracol phenixin of 120～200mL.
High temperature carbonization described in step (2) specifically comprises following operation: the temperature rise rate with 1～10 ℃/min is warming up to 700～1100 ℃, charing 3～5h, then be cooled to 500 ℃ with 3 ℃/min, naturally cool to room temperature.
In step (2), the amount of acetone/hydrochloric acid used/water mixed solvent is that every 1g PSDVB nanometer ball is used 120～400mL.
Described acetone/hydrochloric acid/water mixed solvent is mixed for 2020:76:666 by volume by acetone, hydrochloric acid and water.
Described hydrochloric acid is the hydrochloric acid that volumn concentration is 37%.
Swelling described in step (2) refers at room temperature swelling 12h.
Stirring heating crosslinking reaction described in step (2) refers at 30～78 ℃ of lower stirring reaction 0.25～48h.
Drying described in step (2) refers to dry 12～24h under 120 ℃.
Noble gas atmosphere described in step (2) refers to the nitrogen atmosphere of 200～500mL/min flow velocity.
For realizing better the present invention, preferably, the St monomer described in step (1) and DVB are used syringe dropwise to add in emulsion so that it fully disperses.
Preferably, before the initiator described in step (1) adds, the logical nitrogen 0.5h of mixing solutions is with abundant deoxygenation.
Preferably, the reaction of the heated polymerizable described in step (1) is carried out under nitrogen protection.
Preferably, the device of stirring heating crosslinking reaction described in step (2) is with the drying tube that loads Calcium Chloride Powder Anhydrous.
The application of above-mentioned Powdered charcoal-aero gel in preparing electrode materials, drug release material and sorbing material.
Mechanism of the present invention is:
At first the present invention take St and DVB is reaction raw materials, and P123, SDS or DTAB are emulsifying agent, and distilled water is solvent, and KPS or AIBN are initiator, prepare monodispersed PSDVB nanometer ball.The above-mentioned PSDVB nanometer ball of take is raw material, anhydrous tetracol phenixin is solvent and linking agent, aluminum trichloride (anhydrous) is catalyzer, stirring heating backflow is at a certain temperature carried out the super crosslinking reaction of Friedel-Crafts and is obtained Powdered organic aerogel, and then in inert atmosphere, charing obtains Powdered charcoal-aero gel.Crosslinked and a large amount of mesopores of stacking formation and macropore between the carbon nanospheres ball of this Powdered charcoal-aero gel, mutually run through connection between each duct, formation has stratification nanometer network pore passage structure unique, that three-dimensional is connected, there is synergistic effect between each level nano pore, there is potential application widely in preparing electrode materials, drug release material and sorbing material.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) preparation method of Powdered charcoal-aero gel of the present invention is simple, and no matter the gentle easily control of reaction conditions, be (micro-) letex polymerization, or the carbonyl gelation is crosslinked, is all to carry out under agitation condition, without the implode phenomenon, is conducive to industrialization and amplifies.The charcoal-aero gel presoma (polystyrene-divinylbenzene nanometer ball) that simultaneously prepared by this method but directly carry out drying under condition of normal pressure, simple process, equipment requirements is low.
(2) be different from classical block carbon aerogel material, gained charcoal-aero gel of the present invention is the micron powder shape, in many Application Areass, need not can directly use through ball milling, is conducive to the simplification of application art.
(3) but the superhigh cross-linking chemical structure produced in Friedel-Crafts reaction can be given Carbonization and the inheritability of organic aerogel three-dimensional manometer network structure, and charing is processed and can be produced a large amount of micropores in gel skeleton inside, make the gained charcoal-aero gel there is high-specific surface area, reach as high as 2472m
2more than/g, potential application is widely arranged in preparing electrode materials, drug release material and sorbing material.
(4) the synthetic PSDVB nanometer ball of utilization (micro-) emulsion polymerization technology has highly single the dispersion, and therefore by it, the stacking construction unit of derivative and next charcoal-aero gel also has good sphericity and uniform particle diameter, is conducive to accurately constructing of nanostructure.
The accompanying drawing explanation
Fig. 1 is that the Powdered charcoal-aero gel that embodiment 1 prepares is dispersed in the grain size distribution curve in ethanol.
The nitrogen adsorption that Fig. 2 is the Powdered charcoal-aero gel for preparing of embodiment 1-desorption isotherm figure.
The scanning electron microscope (SEM) photograph that Fig. 3 is the Powdered charcoal-aero gel for preparing of embodiment 1.
The absorption that Fig. 4 is the Powdered charcoal-aero gel for preparing of embodiment 2-elution profiles figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: a kind of preparation of Powdered charcoal-aero gel
(1) in 250ml tetra-neck flasks, add 18.3g P123(to be purchased from Aladdin reagent company) and 160ml distilled water, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer (production of Shanghai chemical reagent work) is purchased to Aladdin reagent company with 0.4g precrosslinker DVB() mix, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 0.7g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 10 ℃/min, be warming up to 1000 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
The Powdered charcoal-aero gel of preparation after dispersed with stirring, is used to the microtexture of the Zeta PALS dynamic laser light scattering apparatus working sample of U.S. Brookhaven company product in ethanol, and the particle diameter and the dispersiveness that obtain are shown in Fig. 1.As seen from Figure 1, prepared charcoal-aero gel is the uniform powder of median size in 2.6 μ m left and right.The particle diameter of PSDVB nanometer ball is 36nm.
The pore structure of the Powdered charcoal-aero gel of ASAP2020 adsorption instrument nitrogen adsorption method test gained produced with U.S. Micromeritics company, resulting N
2as shown in Figure 2, its specific surface area (BET) is 2472m to the adsorption-desorption thermoisopleth
2/ g, wherein micropore and external holes specific surface area are respectively 949m
2/ g and 1523m
2/ g.The scanning electron microscopic observation structure shows (Fig. 3), and the Powdered charcoal-aero gel of gained, by stacking the forming of carbon nanospheres covalency of particle diameter 30nm left and right, is typical aerogel material, has unique three-dimensional manometer network structure.
The ASAP2010 adsorption instrument CO produced with U.S. Micromeritics company
2the Powdered charcoal-aero gel of absorption method test gained at 0 ℃ to CO
2adsorptive capacity be 121cm
3/ g.
Embodiment 2: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 1 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.2 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 647m
2/ g.
The Powdered charcoal-aero gel of the gained of take is electrode materials, take potassium hydroxide as electrolytic solution, is assembled into chemical condenser, and charging and discharging electrical method with crossing current, to record its quality be 88F/g than electric capacity.
The Powdered charcoal-aero gel of the gained of take is sorbent material, and the captopril solution of 2g/L of take is adsorbate, and absorption-elution profiles as shown in Figure 4.This Powdered charcoal-aero gel is at room temperature 50wt% to the adsorptive capacity of captopril solution, in the burst size that discharges 120h, is 49wt%.
Embodiment 3: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 0.7g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 1 ℃/min, be warming up to 1000 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 3.1 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 1901m
2/ g.
Embodiment 4: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 0.7g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 10 ℃/min, be warming up to 900 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.6 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 1300m
2/ g.
Embodiment 5: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 0.7g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 1 ℃/min, be warming up to 900 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 3.3 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 1262m
2/ g.
Embodiment 6: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 1100 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.7 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 294m
2/ g.
Embodiment 7: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 1000 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 3.7 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 463m
2/ g.
Embodiment 8: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%, and water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 900 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 3.5 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 500m
2/ g.
Embodiment 9: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.9 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 486m
2/ g.
Embodiment 10: a kind of preparation of Powdered charcoal-aero gel
(1) add 18.3g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 700 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.7 μ m left and right, and PSDVB nanometer ball particle diameter is 36nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 487m
2/ g.
Embodiment 11: a kind of preparation of Powdered charcoal-aero gel
(1) add 12.4g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 3.3 μ m left and right, and PSDVB nanometer ball particle diameter is 56nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 395m
2/ g.
Embodiment 12: a kind of preparation of Powdered charcoal-aero gel
(1) add 8.7g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.7 μ m left and right, and PSDVB nanometer ball particle diameter is 88nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 506m
2/ g.
Embodiment 13: a kind of preparation of Powdered charcoal-aero gel
(1) add 1.7g P123 and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2.2 μ m left and right, and PSDVB nanometer ball particle diameter is 160nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 544m
2/ g.
Embodiment 14: a kind of preparation of Powdered charcoal-aero gel
(1) add 0.16g SDS, 8g amylalcohol and 160ml distilled water in 250ml tetra-neck flasks, be stirred to it and dissolve fully.Pass into nitrogen in gained solution, after 10min, 4.0g St monomer is mixed with 0.9g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 80 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 12h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 900 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 2785nm, and PSDVB nanometer ball particle diameter is 57nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 900m
2/ g.
Embodiment 15: a kind of preparation of Powdered charcoal-aero gel
(1) add 8g DTAB and 160ml distilled water in 250ml tetra-neck flasks, be stirred to P123 and dissolve fully.Pass into nitrogen in gained solution, after 30min, 4.0g St monomer is mixed with 0.4g precrosslinker DVB, dropwise add gained solution with the 10ml syringe, after mechanical stirring is uniformly dispersed, setting temperature of reaction is 70 ℃, add 0.04g KPS after temperature-stable, stirring heating refluxes, and stir speed (S.S.) is 270r/min, carries out Raolical polymerizable 3h.
(2) after having reacted, the gained emulsion is joined in 500ml methyl alcohol, standing extremely white floss separates with supernatant liquid, and floss is centrifugal, after washing, in 50 ℃ of dry 12h, obtains monodispersed PSDVB nanometer ball.
(3) add the dried PSDVB nanometer ball of 0.5g and the anhydrous tetracol phenixin of 60ml in the 100ml three-necked bottle, be stirred to its complete swelling, then setting temperature of reaction is 75 ℃, adds the 1.4g aluminum trichloride (anhydrous), 75 ℃ of lower stirring heating, refluxes and carries out Friedel-Crafts reaction 24h.
(4) add acetone/hydrochloric acid/water mixed solvent 60ml to stop the Friedel-Crafts reaction, obtain Powdered organic aerogel after suction filtration, washing and constant pressure and dry; Hydrochloric acid is the hydrochloric acid that volumn concentration is 37%; Water is distilled water.
(5) the gained organic aerogel is loaded and to be placed in charring furnace with the magnetic boat, under the nitrogen atmosphere of 400ml/min flow velocity, with the temperature rise rate of 5 ℃/min, be warming up to 800 ℃, constant temperature charing 3h, then 3 ℃/min is cooled to 500 ℃, then naturally cools to room temperature, obtains Powdered charcoal-aero gel.
By the PSDVB nanometer ball of preparation and Powdered charcoal-aero gel in ethanol after dispersed with stirring, the Zeta PALS dynamic laser light scattering apparatus produced with U.S. Brookhaven company is measured, can obtain prepared charcoal-aero gel median size is 893nm, and PSDVB nanometer ball particle diameter is 30nm.
The ASAP2010 adsorption instrument nitrogen adsorption method test of producing with U.S. Micromeritics company, the specific surface area of the Powdered charcoal-aero gel of gained (BET) is 375m
2/ g.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a Powdered charcoal-aero gel is characterized in that: crosslinked stacking the forming of the carbon nanospheres construction unit that is 20～300nm by particle diameter, and there are a large amount of micropores on the carbon nanospheres surface, and its specific surface area is 294～2472m
2/ g.
2. the preparation method of a Powdered charcoal-aero gel according to claim 1 is characterized in that comprising following concrete steps:
(1) preparation of polystyrene-divinylbenzene nanometer ball: tensio-active agent is added to the water, is stirred to fully and dissolves, add St monomer and Vinylstyrene, after being uniformly dispersed, add initiator, the heated polymerizable reaction; Alcohol precipitation, after centrifugal, washing, drying, obtain the polystyrene-divinylbenzene nanometer ball;
(2) step (1) gained polystyrene-divinylbenzene nanometer ball is added in anhydrous tetracol phenixin, stir swelling; Add aluminum trichloride (anhydrous), the stirring heating crosslinking reaction; Add acetone/hydrochloric acid/water mixed solvent termination reaction, after filtration, washing, drying, obtain organic aerogel; Under the noble gas atmosphere, high temperature carbonization, obtain Powdered charcoal-aero gel.
3. the preparation method of Powdered charcoal-aero gel according to claim 2 is characterized in that: the consumption of tensio-active agent described in step (1) is that every 160mL water is used 0.9～18.3g tensio-active agent; St used: Vinylstyrene: initiator: the mass ratio of tensio-active agent is 4:(0.2～4): (0.04～0.08): (0.16～18.3).
4. the preparation method of Powdered charcoal-aero gel according to claim 2, it is characterized in that: described in step (1), tensio-active agent refers at least one in polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer, sodium lauryl sulphate and Trimethyllaurylammonium bromide; Described initiator refers to Potassium Persulphate or Diisopropyl azodicarboxylate.
5. the preparation method of Powdered charcoal-aero gel according to claim 2 is characterized in that: the consumption of described tensio-active agent is that every 160mL water is used the 18.3g tensio-active agent; Described tensio-active agent refers to polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer; Described initiator refers to Potassium Persulphate.
6. the preparation method of Powdered charcoal-aero gel according to claim 2 is characterized in that: the heated polymerizable reaction described in step (1) refers at 70～80 ℃ of reaction 3～24h; Described alcohol precipitation refers to add methyl alcohol, makes product form throw out precipitate and separate; Described drying refers to dry 12～24h under 50 ℃.
7. the preparation method of Powdered charcoal-aero gel according to claim 2, it is characterized in that: in step (2), the mass ratio of polystyrene-divinylbenzene nanometer ball used and aluminum trichloride (anhydrous) is 0.5:(0.7～2.8); The amount of anhydrous tetracol phenixin used is that every 1g polystyrene-divinylbenzene nanometer ball is used the anhydrous tetracol phenixin of 120～200mL; The amount of acetone/hydrochloric acid used/water mixed solvent is that every 1g polystyrene-divinylbenzene nanometer ball is used 120～400mL; Described acetone/hydrochloric acid/water mixed solvent is mixed for 2020:76:666 by volume by acetone, hydrochloric acid and water.
8. the preparation method of Powdered charcoal-aero gel according to claim 2, it is characterized in that: the high temperature carbonization described in step (2) specifically comprises following operation: the temperature rise rate with 1～10 ℃/min is warming up to 700～1100 ℃, charing 3～5h, be cooled to 500 ℃ with 3 ℃/min again, naturally cool to room temperature.
9. the preparation method of Powdered charcoal-aero gel according to claim 2, it is characterized in that: the swelling described in step (2) refers at room temperature swelling 12h; Described stirring heating crosslinking reaction refers at 30～78 ℃ of lower stirring reaction 0.25～48h; Described drying refers to dry 12～24h under 120 ℃; Described noble gas atmosphere refers to the nitrogen atmosphere of 200～500mL/min flow velocity.
10. the application of Powdered charcoal-aero gel according to claim 1 in preparing electrode materials, drug release material and sorbing material.
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