CN1821182A - Method for preparing mesoporous carbon material - Google Patents
Method for preparing mesoporous carbon material Download PDFInfo
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- CN1821182A CN1821182A CN 200610023663 CN200610023663A CN1821182A CN 1821182 A CN1821182 A CN 1821182A CN 200610023663 CN200610023663 CN 200610023663 CN 200610023663 A CN200610023663 A CN 200610023663A CN 1821182 A CN1821182 A CN 1821182A
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Abstract
The present invention belongs to the field of material preparing technology. By means of sol-gel technology, organic high molecule and silicon source are led into a surfactant self-assembling reaction system so as to prepare high ordered mesoporous high molecule/silica and carbon/silica composite material and ordered mesoporous carbon material through organic-organic competition, inorganic-inorganic competition, organic-inorganic competition, cross-linking polymerization coordinate assembling and solvent volatizing self assembling. The prepared mesoporous carbon material has high order property, great specific surface area, great caliber and great porosity, as well as excellent electrochemical properties as super capacitor and cell material. It has also wide application foreground in catalysis, adsorption, biomolecule separation, and other fields.
Description
Technical field
The invention belongs to technical field of material, be specifically related to utilize colloidal sol-gel technique that organic polymer and silicon source introducing tensio-active agent self-assembling reaction system are prepared novel mesoporous material novel method.Pretend usefulness by vying each other between organic-organic and inorganic-inorganic and organic-inorganic, polymerization crosslinking and coordinated groups, the solvent evaporates self-assembly prepares the mesoporous polymer/silicon-dioxide of high-sequential and carbon/silicon dioxide composite material and high-ratio surface, wide-aperture meso-porous carbon material.
Technical background
The organic-inorganic matrix material not only has characteristics such as the easy modification, snappiness height of organic materials, and simultaneously, the interpolation of inorganics has also improved its thermostability, physical strength and physicochemical property.Mesoporous organic-inorganic matrix material is owing to have unique physics, chemical property and unique nanometer steric effect, in many fields such as the absorption of the separation of catalysis, absorption, biomolecules, gas sensitive, opto-electronic device, biological enzyme, fuel molecule and electric double layer capacitances wide application prospect arranged.According to existence form and the interaction between organic composition and the inorganic composition, the method of present synthesising mesoporous organic-inorganic matrix material has: 1. molecular level is compound: adopting the organosilicon that contains the polymerizable organo-functional group is presoma, in established inorganic network, form organic network by photochemistry or thermal treatment, obtain molecular level compound periodic mesoporous organic silicon oxide material (PMO).But the organosilicon source of use is relatively more expensive, does not utilize large batch of production; 2. nanometer level is compound: add high polymer monomer in Metaporous silicon dioxide material, form macromolecule layer by in-situ polymerization in the duct of inorganic mesoporous material, obtain the organic-inorganic matrix material that polymer coats.Up to the present, also there is not simple, economic method to synthesize the mesoporous organic-inorganic matrix material of nanometer level compound.
Meso-porous nano carbon/silicon dioxide composite material is because the duct of its high specific surface, rule can be used as catalyzer, support of the catalyst, aspects such as separation in catalysis, absorption, biomolecules have wide application value, simultaneously, these matrix materials and nano-carbon material have tempting application prospect at aspects such as the absorption of gas sensitive, opto-electronic device, biological enzyme, fuel molecule and electric double layer capacitances.Compare with simple carbon material, the existence of silicon-dioxide has not only strengthened the physical strength of material, avoided simultaneously in actual applications because the shortcoming that current density and the Pt of load are not directly proportional in the fuel cell that the self-cohesion action of carbon granule causes, so the battery electrode that acts as a fuel is applied to the electrochemical catalysis aspect and has demonstrated outstanding performance.Simultaneously, because nano-sized carbon/silicon dioxide composite material has easy synthetic, nontoxic and to advantages such as ambient stables, have important use value aspect solar absorption.Traditional solar absorber is to be matrix with the porous material, and deposition dye molecule or metallic particles as Ni, Co, Cr or the like, and show high sunlight specific absorption (α ≈ 0.96) and low thermal emissivity (ε ≈ 0.12) between room temperature to 100 ℃.Yet the optical characteristics of these materials is along with the increase of cycle index reduces gradually, and many metals can be easily oxidized under high temperature, humidity condition, thereby reduces the absorption to sunlight.Simultaneously, these materials partly be deleterious, can not recycle, will inevitably bring environmental problem.Therefore, for fear of the shortcoming that present solar absorber exists, need to seek a kind ofly be easy to get, nontoxic, and the solar absorber novel to ambient stable, mesoporous carbon/silicon dioxide composite material satisfies this requirement.But previous resulting nano-sized carbon/silicon dioxide composite material all is unordered, vermiform holes, presses for synthetic a kind of mesoporous carbon/silicon dioxide composite material with orderly duct.
Ordered mesoporous carbon material is an emerging in recent years class mesoporous material, have characteristics such as high-ratio surface, wide aperture, these special nature have been given aspects such as the absorption of the separation of meso-porous carbon material in catalysis, absorption, biomolecules, biological enzyme, fuel molecule and electric double layer capacitance great application prospect.At present, people adopt hard template method to prepare meso-porous carbon material usually, are specially 1) prepare the ordered mesoporous silica dioxide material earlier, as SBA-15, MCM-48, KIT-6 etc.; 2) with the mesoporous silicon oxide be hard template,, the higher carbon sources of carbon residue rate such as sucrose, furfuryl alcohol inserted in the orderly nano pore of mesopore silicon oxide by the method for nanometer cast; 3) by high temperature cabonization, hydrofluoric acid dissolution is removed silica template, obtains mesoporous carbon at last.The mesoporous carbon that this synthetic method obtains is that the replisome of original silicon template has the mesoscopic structure anti-phase with silicon-dioxide.In addition, it is loaded down with trivial details that hard template method prepares the meso-porous carbon material process, of a high price.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of simple, with low cost meso-porous carbon material.
The present invention is by organic-synthesizing ordered mesoporous polymer of organic self-assembly, further carbonization obtain having open architecture, with the meso-porous carbon material of mesopore silicon oxide same structure.Simultaneously, compare with the synthesising mesoporous carbon material of traditional hard template method, the soft template single stage method is in synthetic method, and the material structure aspect has its unique advantage, shrink seriously but exist the carbonization process skeleton at present, the meso-porous carbon material that obtains has the low (～1000m of specific surface area
2/ g), the aperture little (～3nm) shortcoming, serious restriction their practical application.In order to address this problem, key is to find a kind of method of simple possible to synthesize the meso-porous carbon material of high-sequential, high-ratio surface, wide aperture and large pore volume.
The present invention utilizes sol-gel technique, organic polymer and silicon source are introduced tensio-active agent self-assembling reaction system, pretend to use by vying each other between organic-organic and inorganic-inorganic and organic-inorganic, polymerization crosslinking and coordinated groups, the solvent evaporates self-assembling method, the mesoporous polymer/silicon-dioxide of preparation high-sequential and carbon/silicon dioxide composite material and high-ratio surface, wide-aperture meso-porous carbon material.
The invention provides a kind of preparation method of meso-porous carbon material.This method is as follows: at first nonionogenic tenside and acid catalyst are dissolved in the organic solvent, make settled solution; In solution, add silicon source and polymer presoma then, it is well dispersed in the organic solvent, stir and make solvent evaporates; After treating that solvent evaporates is fully, low-temperature curing, nonionogenic tenside is removed in the high-temperature roasting under reflux extraction or inert atmosphere of gained solid product, promptly obtains the mesoporous polymer/silicon dioxide composite material of high-sequential;
Used acid catalyst is C
1-C
3Organic acid, oxalic acid, one or more in phenylformic acid or the mineral acid; Used organic solvent is one or more in alcohols, benzene class, tetrahydrofuran (THF), ether, chloroform or the methylene dichloride; Used polymer presoma is resol, polyimide, polypyrrole, polyacrylamide, polyvinylpyridine, and one or more in the polyacrylonitrile, the molecular weight of polymer presoma are 200～5000; The silicon source is organo-silicon ester alkane or inorganic silicon; The concentration that adds nonionogenic tenside in the system is 4-10wt.%; Used polymer presoma and nonionogenic tenside mass ratio are 0.5-2.0; The ratio of the quality in polymer presoma/silicon source from zero to infinity; Catalyzer is 0.2-0.004 with silicon source quality ratio, and the mass ratio in water and silicon source is 1-10; The reactivity scope is 10-60 ℃, and the reaction times is 10 minutes～10 days.
Among the present invention, used tensio-active agent is polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer tensio-active agent.As C
nH
2n+1EO
m, EO
nPO
mEO
n, EO
nBO
mEO
n, EO
nBO
m, EO
nPO
mDeng.The present invention adopts tensio-active agent to synthesize the mesoporous polymer/silicon dioxide composite material of high-sequential as structure directing agent.Method by the solvent evaporates self-assembly, pretend usefulness by vying each other between organic-organic and inorganic-inorganic and organic-inorganic, polymerization crosslinking and coordinated groups, the solvent evaporates self-assembly prepares the mesoporous polymer/silicon-dioxide and the carbon/silicon dioxide composite material of high-sequential.
The used nonionogenic tenside of the present invention mainly includes Brij35 (C
12H
25EO
23), Brij56 (C
16H
33EO
10), Brij78 (C
16H
33EO
20), Brij76 (C
18H
37EO
10),, Brij97 (C
18H
35EO
10), P123 (EO
20PO
70EO
20), P103 (EO
17PO
56EO
17), L121 (EO
5PO
70EO
5), P85 (EO
26PO
39EO
26), P65 (EO
20PO
30EO
20), F127 (EO
106PO
70EO
106), F88 (EO
100PO
39EO
100), F98 (EO
123PO
47EO
123), F108 (EO
132PO
50EO
132), B50-6600 (EO
39BO
47EO
39), B70-4600 (EO
15BO
45EO
15), B40-1900 (EO
13BO
11EO
13), B20-3800 (EO
34BO
11EO
34) etc.The duct spatial symmetry of obtained product can be a three-dimensional cubic structure, and spacer comprises Ia-3d, Im-3m, Pm-3m, three-dimensional hexagonal structure, and spacer comprises P6
3/ mmc, or two-dimentional hexagonal structure, spacer comprises the p6m structure.
Among the present invention, used acid catalyst is a formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid, one or more in the phosphoric acid.Acid catalyst adds in the solution with the form of the aqueous solution.
The present invention utilizes the volatilization of organic solvent to induce the nonionogenic tenside self-assembly to form the meso-hole structure of high-sequential.Used organic solvent can be a protic solvent, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, tetrahydrofuran (THF) or the like, also can be non-protonic solvent, as benzene, toluene, ether, chloroform, methylene dichloride etc.
Among the present invention, adopt the precursor of polymer performed polymer as the synthetic macromolecule mesoporous material, it is lower at the initial reaction stage molecular weight, can well be dissolved in organic solvent, forms the homogeneous system with organic solvent, nonionogenic tenside.Solvent evaporates is increased to temperature of reaction after inducing mesoscopic structure to form, and the polymer presoma is commissure further, finally obtains insoluble infusible macromolecular material.Used macromolecular material is compared with nonionogenic tenside has higher thermostability or chemical stability.
Among the present invention, used polymer presoma can be business-like polymer presoma, also can use homemade polymer oligopolymer presoma.They can be resol, polyimide, polypyrrole, polyacrylamide, polyvinylpyridine, polyacrylonitrile etc.High molecular precursor molecule amount is generally between 200～5000.
Among the present invention, the oil soluble silicon species that adopts the may command hydrolysis is as the silicon source, by the size and the shape of control reaction conditions modulation hydrolysis and polycondensation degree and then modulation silica dioxide granule.Thereby the ratio in silicon dioxide region and polymer zone in orderly mesoporous polymer/silicon-dioxide that modulation obtains and the carbon/silicon dioxide composite material, the just compound level of their molecule.Simultaneously, the mesoporous size of secondary and then on the resulting carbon mesoporous material of the modulation wall.
Among the present invention, the silicon source of used may command hydrolysis can be an organo-silicon ester alkane, as positive quanmethyl silicate (Si (CH
3O)
4), positive tetraethyl orthosilicate (Si (C
2H
5O)
4), positive silicic acid orthocarbonate (Si (n-C
3H
7O)
4), positive silicic acid four isopropyl esters (Si (i-C
3H
7O)
4), positive silicic acid four butyl esters (Si (n-C
4H
9O)
4) or its mixture; Also can be the inorganic silicon source, as water glass (Na
2SiO
4) etc.
Among the present invention, the mass ratio from 0.15 to 10 in polymer presoma and silicon source.
The processing in silicon source can be under acidic conditions, and the reactivity temperature range is 10-60 ℃, and the reaction times is 10 minutes～10 days.Reaction comprises prehydrolysis and polycondensation.
Among the present invention, adopt the high-temperature roasting method under solution reflux extraction method or the inert atmosphere protection to remove nonionogenic tenside.The used solvent of solution reflux extraction method is a sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, a kind of in the potassium hydroxide.The maturing temperature of high-temperature roasting method is 350-500 ℃.Promptly obtain mesoporous polymer/silicon dioxide composite material.
Among the present invention, mesoporous polymer/silicon dioxide composite material that above-mentioned preparation method is obtained further in 800 ℃ of-1400 ℃ of roastings under the inert atmosphere or with the direct high temperature cabonization under inert atmosphere of nonionogenic tenside/polymer/silicon dioxide composite material, promptly gets the mesoporous carbon/silicon dioxide composite material of high-sequential; The roasting carbonization temperature is 350-1400 ℃; Heat-up rate is 1-5 ℃/minute.
In the present invention, the above-mentioned mesoporous carbon/silicon dioxide composite material that obtains can be removed the silicon oxide composition with hydrofluoric acid solution or sodium hydroxide solution drip washing.At room temperature promptly, add the hydrofluoric acid solution (for example 10wt.%HF) of 9-12wt.% or the sodium hydroxide solution of 1-4M, and stir and spend the night (as 24 hours), after filtration, washing and the drying, obtain ordered mesoporous carbon material.
The aperture of the meso-porous carbon material of the present invention's preparation is 7.0-10.0nm, and the pore volume scope is 0.6-1.2cm
3/ g, specific surface are 400-800m
2/ g; The aperture of mesoporous carbon/earth silicon material can be 5.0-8.0nm, pore volume 0.2-0.6cm
3/ g, specific surface are 200-400m
2/ g; The aperture of the ordered mesoporous carbon material that obtains is 5.0-8.0nm, and pore volume is 1.0-2.5cm
3/ g, specific surface are 1000-2400m
2/ g.
Method of the present invention is simple.By the meso-porous carbon material high-sequential that the present invention makes, specific surface height (～2400m
2/ g), the aperture big (～8nm), the big (～2.2m of pore volume
3/ g).These novel meso-porous carbon materials are demonstrating good properties aspect the electrochemistry ultra capacitor battery material, and electrical capacity is 120-200F/g in the aqueous systems, and electrical capacity is 90-130F/g in the organic system.This ordered mesoporous carbon material simultaneously has broad application prospects at aspects such as the absorption of the separation of catalysis, absorption, biomolecules, biological enzyme, fuel molecule and electrode materialss.
Description of drawings
Fig. 1 is the feature XRD figure spectrum of the mesoporous polymer/silicon dioxide composite material of two dimension six side p6m structures.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the reaction system of shop film by the solvent evaporates self-assembly is by the feature XRD figure spectrum of the mesoporous polymer/silicon dioxide composite material of the resulting two-dimentional six side p6m structures of roasting under solvent extraction or the 350 ℃ of nitrogen atmospheres.
Fig. 2 is the feature nitrogen adsorption-desorption isotherm figure of the mesoporous polymer/silicon dioxide composite material of two dimension six side p6m structures.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, the feature nitrogen adsorption-desorption isotherm of the mesoporous polymer/silicon dioxide composite material of resulting two-dimentional six side p6m structures.
Fig. 3 is the feature holes distribution curve of the mesoporous polymer/silicon dioxide composite material of two dimension six side p6m structures.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, the pore distribution curve of the mesoporous polymer/silicon dioxide composite material of resulting two-dimentional six side p6m structures.
Fig. 4 is the mesoporous carbon/silicon dioxide composite material of two dimension six side p6m structures and feature small angle X ray scattering (SAXS) collection of illustrative plates of meso-porous carbon material.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, feature small angle X ray scattering (SAXS) collection of illustrative plates of the mesoporous carbon/silicon dioxide composite material of resulting two-dimentional six side p6m structures and meso-porous carbon material.
Fig. 5 is the mesoporous carbon/silicon dioxide composite material of two dimension six side p6m structures and the feature nitrogen adsorption-desorption isotherm figure of meso-porous carbon material.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, the feature nitrogen adsorption-desorption isotherm figure of the mesoporous carbon silicon dioxide composite material of resulting two-dimentional six side p6m structures and meso-porous carbon material.
Fig. 6 is the mesoporous carbon/silicon dioxide composite material of two dimension six side p6m structures and the feature holes distribution curve of meso-porous carbon material.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by reaction system, the mesoporous carbon/silicon dioxide composite material of resulting two-dimentional six side p6m structures and the feature holes distribution curve of meso-porous carbon material of solvent evaporates self-assembly.
Fig. 7 be two dimension six side p6m structures the mesoporous carbon silicon dioxide composite material (A, B) and meso-porous carbon material (C, D) feature TEM schemes.Under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir and spread the reaction system of film after 2 hours by the solvent evaporates self-assembly, mesoporous carbon/silicon dioxide composite material (A of resulting two-dimentional six side p6m structures, B) and meso-porous carbon material (C, D) feature TEM figure.
Fig. 8 is feature small angle X ray scattering (SAXS) collection of illustrative plates of the mesoporous polymer/silicon dioxide composite material of two dimension six side p6m structures.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, feature small angle X ray scattering (SAXS) collection of illustrative plates of the mesoporous polymer/silicon dioxide composite material of resulting two-dimentional six side p6m structures.
Fig. 9 be two dimension six side p6m structures mesoporous carbon/silicon dioxide composite material (A, B) and the mesoporous carbon of diplopore model (C, D, E, feature TEM figure F).Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir and spread the reaction system of film after 5 hours by the solvent evaporates self-assembly, mesoporous carbon/silicon dioxide composite material (H of resulting two-dimentional six side p6m structures, I) and the mesoporous carbon (J of diplopore model, K, L, feature TEM figure M).
Figure 10 is the feature nitrogen adsorption-desorption isotherm of the mesoporous carbon of two dimension mesoporous carbon/silicon dioxide composite material of six side p6m structures and diplopore model.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir and spread film after 5 hours, by the reaction system of solvent evaporates self-assembly, the feature nitrogen adsorption-desorption isotherm of the mesoporous carbon/silicon dioxide composite material of resulting two-dimentional six side p6m structures and the mesoporous carbon of diplopore model.
Figure 11 is the feature holes distribution curve of the mesoporous carbon of two dimension mesoporous carbon/silicon dioxide composite material of six side p6m structures and diplopore model.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g0.2M, 10.0g dehydrated alcohol, 2.5g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir and spread film after 5 hours, by the reaction system of solvent evaporates self-assembly, the feature holes distribution curve of the mesoporous carbon/silicon dioxide composite material of resulting two-dimentional six side p6m structures and the mesoporous carbon of diplopore model.
Figure 12 is feature small angle X ray scattering (SAXS) collection of illustrative plates of the mesoporous carbon of three-dimensional co-continuous cube Ia3d structure.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.0g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 5 hours, the shop film is by the reaction system of solvent evaporates self-assembly, the little angle of feature X-ray scattering (SAXS) collection of illustrative plates of the mesoporous carbon of resulting three-dimensional co-continuous cube Ia3d structure.
Figure 13 is the feature nitrogen adsorption-desorption isotherm figure and the pore distribution curve of the mesoporous carbon of three-dimensional co-continuous cube Ia3d structure.Promptly under 40 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 10.0g dehydrated alcohol, 2.0g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 5 hours the reaction system of shop film, obtain having the feature nitrogen adsorption-desorption isotherm and the pore distribution curve of the mesoporous carbon of three-dimensional co-continuous cube Ia3d structure by the solvent evaporates self-assembly.
Figure 14 is the C-V curve under the mesoporous carbon different condition of two dimension six side p6m structures, and promptly under 25 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 8.0g dehydrated alcohol, 5.0g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir and spread the reaction system of film after 2 hours, obtain the mesoporous carbon (S of two dimension six side p6m structures by the solvent evaporates self-assembly
BET=1507m
2G) be in the electrolytical three-electrode system at the 1.0M NaOH aqueous solution, and the C-V curve under the different sweep velocitys (5mV/s, 20mV/s, 50mV/s).
Figure 15 is the mesoporous carbon capacitance-voltage figure of two dimension six side p6m structures.Promptly under 25 ℃ of conditions, raw material is 1.0g F127 (EO
106PO
70EO
106), the hydrochloric acid soln of 1.0g 0.2M, 8.0g dehydrated alcohol, 5.0g mass percentage concentration be that the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer formed, stir after 2 hours, the shop film is by the reaction system of solvent evaporates self-assembly, the mesoporous carbon (S that obtains having two dimension six side p6m structures
BET=1507m
2/ g) at 1.0M LiPF
6Organic solution is under the ionogen condition, takes continuous current (60mA/g) mode, and voltage range is 0-3V.
Embodiment
Embodiment 1, the preparation condition of resol performed polymer is as follows: with fusion under 45 ℃ of conditions of 32.0g phenol, adding the 7.0g mass percentage concentration is the 20wt.%NaOH aqueous solution and 56.64g formaldehyde solution (37wt.%), refluxed 1 hour down at 65-70 ℃, behind the cool to room temperature, regulate about pH=7 with the 0.6M hydrochloric acid soln, reaction system is placed be lower than 50 ℃ of water-bath underpressure distillation and dewater, obtain 24.8g polymer presoma (molecular weight 200-500).Resulting 24.8g polymer performed polymer is dissolved in the 99.2g ethanol, and the ethanolic soln of resol performed polymer that is configured to mass percentage concentration and is 20wt.% is standby.
Embodiment 3, under 40 ℃ of conditions of polymer/silicon dioxide composite material of two dimension six sides (p6m) structure, with 1.0g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in the 10.0g dehydrated alcohol, stirring makes settled solution, adding the 2.5g mass percentage concentration in this solution is the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer, stirred 2 hours, and made TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, left standstill volatilization under the room temperature, be placed on the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtained 1.75g F127/ polymer/silicon dioxide composite material in 5-10 hour.With the 350 ℃ of roastings 2 hours under nitrogen atmosphere of the matrix material after the polymerization, promptly get 0.8g mesoporous polymer/silicon dioxide composite material (wherein high molecular quality percentage composition is 52wt.%, and the quality percentage composition of silicon is 48wt.%).The aperture of this material is 8.0nm, and pore volume is 0.80cm
3/ g, specific surface area is 440m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 7, under 25 ℃ of conditions of mesoporous carbon/silicon dioxide composite material of two dimension six sides (p6m) structure, with 1.0g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in the 10.0g dehydrated alcohol, stirring makes settled solution, adding the 2.5g mass percentage concentration in this solution is the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer, stirred 2 hours, and made TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, left standstill volatilization under the room temperature, be placed on the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtained 1.65g F127/ polymer/silicon dioxide composite material in 5-10 hour.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of 1.65g F127/ polymer/silicon dioxide composite material, promptly get 0.68g mesoporous carbon/silicon dioxide composite material (wherein the quality percentage composition of carbon is 35wt.%, and the quality percentage composition of silicon is 65wt.%).The aperture of this material is 6.0nm, and pore volume is 0.48cm
3/ g, specific surface area is 307m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 9, under 25 ℃ of conditions of meso-porous carbon material of two dimension six sides (p6m) structure, with 1.0g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 4.0g 0.2M in the 10.0g dehydrated alcohol, stirring makes settled solution, adding the 2.5g mass percentage concentration in this solution is the alcoholic solution and the 2.08g tetraethoxy (TEOS) of 20wt.% resol performed polymer, stirred 2 hours, and made TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, left standstill volatilization under the room temperature, be placed on the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtained 1.75g F127/ polymer/silicon dioxide composite material in 5-10 hour.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of 1.65g F127/ polymer/silicon dioxide composite material or 1.0g mesoporous polymer/silicon dioxide composite material, promptly get 0.72g mesoporous carbon/silicon dioxide composite material.Resulting 0.72g mesoporous carbon/silicon dioxide composite material is placed 10%HF solution, and stirring at room 24 hours is filtered, and drying obtains the meso-porous carbon material that 0.24g has open architecture.The aperture of this material is 5.8nm, and pore volume is 2.07cm
3/ g, specific surface area is 2040m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 12, and the meso-porous carbon material of two dimension six sides (p6m) structure is under 25 ℃ of conditions, with 1.6g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in 8.0g ethanol, stir and make settled solution, in this solution, add alcoholic solution and the 2.08g TEOS that 10.0g contains 20% resol performed polymer, stirred 2 hours, make TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, and room temperature leaves standstill volatilization, places the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtains 2.3gF127/ polymer/silicon dioxide composite material in 5-10 hour.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of 2.3g F127/ polymer/silicon dioxide composite material, promptly obtain 0.75g mesoporous carbon/silicon dioxide composite material resulting 0.75g mesoporous carbon/silicon dioxide composite material is placed 10%HF solution, stirring at room 24 hours, behind the filtration drying, obtain the meso-porous carbon material that 0.45g has open architecture.The aperture of this material is 6.7nm, and pore volume is 1.94cm
3/ g, specific surface area is 1507m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 13, and the polymer/silicon dioxide composite material of two dimension six sides (p6m) structure is under 25 ℃ of conditions, with 2.3g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in 5.0g ethanol, stir and make settled solution, in this solution, add alcoholic solution and the 2.08g TEOS that 10.0g contains 20% resol performed polymer, stirred 2 hours, make TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, and room temperature leaves standstill volatilization, places the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtains 4.5g F127/ polymer/silicon dioxide composite material in 5-10 hour.With the 350 ℃ of roastings 2 hours under nitrogen atmosphere of 4.5g F127/ polymer/silicon dioxide composite material, promptly obtain 2.2g polymer/silicon dioxide composite material (wherein high molecular quality percentage composition is 65wt.%, and the quality percentage composition of silicon is 35wt.%).The aperture of this material is 8.2nm, and pore volume is 1.2cm
3/ g, specific surface area is 650m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 14, and the mesoporous carbon/silicon dioxide composite material of two dimension six sides (p6m) structure is under 25 ℃ of conditions, with 2.3g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in 5.0g ethanol, stir and make settled solution, in this solution, add alcoholic solution and the 2.08g TEOS that 10.0g contains 20% resol performed polymer, stirred 2 hours, make TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, and room temperature leaves standstill volatilization, places the further polymerization in 24 hours of 100 ℃ of baking oven internal heating, and obtains 4.5g F127/ polymer/silicon dioxide composite material in 5-10 hour.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of 4.5g F127/ polymer/silicon dioxide composite material, promptly obtain 1.45g mesoporous carbon/silicon dioxide composite material (wherein the quality percentage composition of carbon is 60wt.%, and the quality percentage composition of silicon is 40wt.%).The aperture of this material is 6.0nm, and pore volume is 0.57cm
3/ g, specific surface area is 385m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 16, and the meso-porous carbon material of two dimension six sides (p6m) structure of diplopore model is under 40 ℃ of conditions, with 1.0g F127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in 10.0g ethanol, stir and make settled solution, in this solution, add the alcoholic solution and the 2.08g TEOS of 2.5g 20% resol performed polymer, stirred 5 hours, make TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred in the watch-glass, and room temperature left standstill volatilization 20-30 hour, placed 100 ℃ of baking oven internal heating to advance polymerization in 40 hours then and obtained 1.6g F127/ polymer/silicon dioxide composite material.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of 1.6g F127/ polymer/silicon dioxide composite material, promptly obtain 0.8g mesoporous carbon/silicon dioxide composite material.Then 0.8g mesoporous carbon/silicon dioxide composite material is placed 10%HF solution, stirring at room 24 hours obtains the meso-porous carbon material that 0.256g has open architecture behind the filtration drying.The diplopore that is of this material distributes, and the aperture is respectively 2.56nm and 5.80nm, and pore volume is 1.72cm
3/ g, specific surface area is 1512m
2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 17, and the meso-porous carbon material of three-dimensional cubic (Ia-3d) structure is under 40 ℃ of conditions, with 1.0gF127 (EO
106PO
70EO
106) and the dissolve with hydrochloric acid solution of 1.0g 0.2M in 10.0g ethanol, stir and make settled solution, in this solution, add the alcoholic solution and the 2.08g TEOS of 2.0g 20% resol performed polymer, stirred 5 hours, make TEOS carry out preliminary hydrolysis and polycondensation.Solution is transferred to the thick film of one-tenth in the watch-glass, and 10 ℃ leave standstill volatilization 20 hours, place the further polymerization in 40 hours of 100 ℃ of baking oven internal heating to obtain 1.84g F127/ polymer/silicon dioxide composite material then.With the 900 ℃ of roastings 2 hours under nitrogen atmosphere of the material after the polymerization, promptly get 0.80g mesoporous carbon/silicon dioxide composite material (wherein the quality percentage composition of carbon is 28wt.%, and the quality percentage composition of silicon is 72wt.%).。Resulting 0.80g carbon/silicon dioxide composite material is placed 10%HF solution, and stirring at room 24 hours is filtered, and drying obtains the meso-porous carbon material that 0.224g has open architecture.The aperture of this material is 4.6nm, has been full of mesoporous about 2.6nm on the wall, and pore volume is 1.4cm
3/ g, specific surface area is 1400m
2/ g, the duct spatial symmetry of material are a cube Ia3d structure.
Embodiment 18, and (spacer is p6m, S with the mesoporous carbon of 80wt.% in the application of meso-porous carbon material aqueous systems on electrochemical capacitor of two dimension six sides (p6m) structure
BET=1507m
2/ g), the tetrafluoroethylene of the acetylene black of 10wt.%, 10wt.% is pressed on the nickel screen after mixing, and 120 ℃ of dryings 12 hours, electrode density is 5mg/cm
2The water system electro-chemical test adopts three-electrode system, is working electrode with the carbon dioxide process carbon electrode, and saturated calomel electrode (SCE) is as reference electrode, and the Pt sheet is a counter electrode, and electrolytic solution is the 2.0M KOH aqueous solution.-0.1 ~-1.0V (VS.SCE) potential range in, sweep speed and increase to 50mV/s, current-voltage curve is still kept good parallelogram.Corresponding to sweeping fast 5mV/s, 20mV/s, the electrical capacity that 50mV/s calculates is respectively and is 181F/g, 176F/g, 164F/g has power-performance preferably.
Embodiment 19, the meso-porous carbon material of two dimension six sides (p6m) structure (spacer is p6m, S with the mesoporous carbon of 80wt.% in the application of organic system on electrochemical capacitor
BET=1507m
2/ g), the tetrafluoroethylene of the acetylene black of 10wt.%, 10wt.% is pressed in nickel screen after mixing or aluminium is online, and 120 ℃ of dryings 12 hours, electrode density is 5mg/cm
2The capacitive properties test of organic system is that two carbon dioxide process carbon electrodes are assembled into double layer capacitor according to carbon/barrier film/carbon, wherein adopts the aluminium net to make current collector as the anodal carbon dioxide process carbon electrode, makees current collector as the carbon dioxide process carbon electrode employing nickel screen of negative pole, and electrolytic solution is 1.0M LiPF
6NSC 11801 (EC) and methylcarbonate (DMC) mixing solutions (wherein the volume ratio of EC/DMC is 1: 2).In 0～3V potential region, charge and discharge with the current density of 60mA/g, the capacity of mesoporous carbon is 110F/g (calculation of capacity is based on the quality of mesoporous carbon in the single electrode).
Claims (13)
1. the preparation method of a meso-porous carbon material, it is characterized in that: this method is as follows: at first nonionogenic tenside and acid catalyst are dissolved in the organic solvent, make settled solution; In solution, add silicon source and polymer presoma then, it is well dispersed in the organic solvent, stir and make solvent evaporates; After treating that solvent evaporates is fully, low-temperature curing, nonionogenic tenside is removed in the high-temperature roasting under reflux extraction or inert atmosphere of gained solid product, promptly obtains the mesoporous polymer/silicon dioxide composite material of high-sequential;
Used acid catalyst is C
1-C
3Organic acid, oxalic acid, one or more in phenylformic acid or the mineral acid; Used organic solvent is one or more in alcohols, benzene class, tetrahydrofuran (THF), ether, chloroform or the methylene dichloride; Used polymer presoma is resol, polyimide, polypyrrole, polyacrylamide, polyvinylpyridine, and one or more in the polyacrylonitrile, the molecular weight of polymer presoma are 200～5000; The silicon source is organo-silicon ester alkane or inorganic silicon; The concentration that adds nonionogenic tenside in the system is 4-10wt.%; Used polymer presoma and nonionogenic tenside mass ratio are 0.5-2.0; The ratio of the quality in polymer presoma/silicon source from zero to infinity; Catalyzer is 0.2-0.004 with silicon source quality ratio, and the mass ratio in water and silicon source is 1-10; The reactivity temperature range is 10-60 ℃, and the reaction times is 10 minutes～10 days.
2. preparation method according to claim 1, it is characterized in that: used nonionogenic tenside is polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer tensio-active agent.
3. preparation method according to claim 2 is characterized in that: used nonionogenic tenside is C
12H
25EO
23, C
16H
33EO
10, C
16H
33EO
20, C
18H
37EO
10, C
18H
35EO
10, EO
20PO
70EO
20, EO
17PO
56EO
17, EO
5PO
70EO
5, EO
26PO
39EO
26, EO
20PO
30EO
20, EO
106PO
70EO
10, EO
100PO
39EO
100, EO
123PO
47EO1
23, EO
132PO
50EO
132, EO
39BO
47EO
39, EO
15BO
45EO
15, EO
13BO
11EO
13, EO
34BO
11EO
34Wherein one or more.
4. preparation method according to claim 1 is characterized in that: used acid catalyst is a formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid, one or more in the phosphoric acid.
5. preparation method according to claim 1 is characterized in that: used organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, tetrahydrofuran (THF), perhaps one or more in benzene, toluene, ether, chloroform, the methylene dichloride.
6. preparation method according to claim 1 is characterized in that: used silicon source is one or more in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four isopropyl esters, positive silicic acid four butyl esters, the water glass.
7. preparation method according to claim 1 is characterized in that: the mass ratio from 0.15 to 10 in polymer presoma and silicon source.
8. preparation method according to claim 1 is characterized in that: adopt the high-temperature roasting method under solution reflux extraction method or the inert atmosphere protection to remove nonionogenic tenside.
9. preparation method according to claim 8 is characterized in that: the used solvent of solution reflux extraction method is a sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, a kind of in the potassium hydroxide.
10. preparation method according to claim 8 is characterized in that: the maturing temperature of high-temperature roasting method is 350-500 ℃.
11. preparation method according to claim 1, it is characterized in that: mesoporous polymer/silicon dioxide composite material of obtaining further in 800 ℃ of-1400 ℃ of roastings under the inert atmosphere or with the direct high temperature cabonization under inert atmosphere of nonionogenic tenside/polymer/silicon dioxide composite material, is promptly got the mesoporous carbon/silicon dioxide composite material of high-sequential; The roasting carbonization temperature is 350-1400 ℃; Heat-up rate is 1-5 ℃/minute.
12. preparation method according to claim 11 is characterized in that: the mesoporous carbon/earth silicon material that obtains is removed silicon oxide with hydrofluoric acid solution or sodium hydroxide solution drip washing form; At room temperature promptly, add the hydrofluoric acid solution of 9-12wt.% or the sodium hydroxide solution of 1-4M, and stir and spend the night, after filtration, washing and the drying, obtain ordered mesoporous carbon material.
13. meso-porous carbon material according to claim 1 is characterized in that: the aperture of mesoporous polymer/silicon dioxide composite material is 7.0-10.0nm, and the pore volume scope is 0.6-1.2cm
3/ g, specific surface are 400-800m
2/ g; The aperture of mesoporous carbon/earth silicon material is 5.0-8.0nm, pore volume 0.2-0.6cm
3/ g, specific surface are 200-400m
2/ g; The aperture of the ordered mesoporous carbon material that obtains is 5.0-8.0nm, and pore volume is 1.0-2.5cm
3/ g, specific surface are 1000-2400m
2/ g.
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