CN100395310C - Method of preparing multiporous. polymer or multiporous carbon material with large ratio of surface and high sequence in water solution - Google Patents
Method of preparing multiporous. polymer or multiporous carbon material with large ratio of surface and high sequence in water solution Download PDFInfo
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- CN100395310C CN100395310C CNB2006100243899A CN200610024389A CN100395310C CN 100395310 C CN100395310 C CN 100395310C CN B2006100243899 A CNB2006100243899 A CN B2006100243899A CN 200610024389 A CN200610024389 A CN 200610024389A CN 100395310 C CN100395310 C CN 100395310C
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Abstract
The present invention belongs to the field of material preparation, particularly relates to a method for preparing mesoporous macromolecular material and mesoporous carbon material with high degree of order and large specific surface area in water solution (like hydrothermal condition) with the utilization of organic-organic self-assembly. The preparation method comprises: with the utilization of the self-assembly of nonionic surfactant and macromolecule precursor, the macromolecule precursor can be polymerized further in crosslinking on the periphery of the surfactant in aqueous solution under the condition of certain temperature, concentration and pH value, and stable macromolecule-nonionic surfactant composite material with an ordered mesoscopic structure (a two-dimensional hexagonal or a three-dimensional cubic structure); the surfactant in the macromolecule-nonionic surfactant composite material can be removed by solvent reflux extraction or calcination under inert atmosphere, and the mesoporous macromolecular material with high degree of order and large specific surface area is obtained. Also, further high temperature carbonization can be carried out to the mesoporous macromolecular material under inert atmosphere to obtain the mesoporous carbon material with the corresponding structure; besides, the macromolecule-nonionic surfactant composite material can be directly carbonized to obtain the mesoporous carbon material.
Description
Technical field
The invention belongs to technical field of material, be specifically related to the mesoporous polymer of bigger serface, high-sequential in the class aqueous solution or the preparation method of meso-porous carbon material.
Background technology
Mesopore silicon oxide is an emerging in recent years class material, its duct homogeneous and size adjustable, specific surface height and surface are easy to functionalization, thereby mesopore silicon oxide both can be used as macromolecular sorbent material, also can embody huge application potential at aspects such as absorption, catalysis, separation for all kinds of catalyzed reactions provide a nanometer reaction compartment.
Be different from mesopore silicon oxide, mesoporous polymer and meso-porous carbon material be because its special composition and surface properties, and had special performances more, has been subjected to the extensive concern of scientists.Mesoporous polymer makes its surface easier to be functionalized, the material that obtains having specific function because its special macromolecular scaffold is formed; On the other hand, meso-porous carbon material has good electroconductibility because carbon skeleton is formed, and therefore at aspects such as catalysis, electric double layer capacitance, lithium ion battery, solar cells great application prospect is arranged.For the mesoporous polymer material, traditional preparation method mainly comprises control foaming, particle etching method, molecular imprinting and segmented copolymer self-assembly etching method etc.But above these procedure complexity, and the stability of material that obtains is relatively poor, and structurally ordered degree is not high, and specific surface is low, and pore volume is little.And what mainly adopt for the preparation of meso-porous carbon material is the hard template transfer printing, and process is very loaded down with trivial details, and poisonous contaminative is strong, and of a high price.Recently, there is the investigator successfully to utilize the organic solvent volatilization method,, prepared the mesoporous polymer with two dimension or three-dimensional structure and the carbon material of high-sequential by the self-assembly of control resol and segmented copolymer.Yet solvent evaporation method relatively is fit to the preparation of mould material, is not suitable for the mass preparation of powder body material.In order to address the above problem, key is to find a kind of method of simple possible to prepare mesoporous polymer or its carbon material of high-sequential and Adjustable structure on a large scale.
Summary of the invention
The present invention proposes is that a kind of simple, with low cost specific surface area is big, the degree of order is high and the mesoporous polymer material of Adjustable structure or the preparation method of meso-porous carbon material.
Prepare bigger serface in the aqueous solution that the present invention proposes, the mesoporous polymer of high-sequential and the method for meso-porous carbon material are: a certain amount of nonionogenic tenside is dissolved in has in a certain amount of water, obtain the clarifying aqueous solution, material preparation for some structure also need add a certain amount of organic cosolvent, then with a certain amount of, finite concentration, the high-molecular precursor solution of certain acid-basicity is mixed, react for some time at a certain temperature then, filtration obtains product, product extracted in certain solvent or inert atmosphere under in the certain temperature roasting, can remove the mesoporous polymer that template obtains having two dimension or three-dimensional structure, with the direct high temperature cabonization under inert atmosphere of product, the meso-porous carbon material that can obtain having two dimension or three-dimensional structure.
Among the present invention,, in the aqueous solution of certain potential of hydrogen, utilize the self-assembly of polymer presoma and tensio-active agent and the crosslinking polymerization of polymer presoma, obtain mesoporous polymer or meso-porous carbon material at last by having certain temperature.
The present invention proposes a kind of in the aqueous solution mesoporous polymer of bigger serface, high-sequential or the preparation method of meso-porous carbon material, under hydrothermal condition, utilize organic-organic self-assembly of polymer presoma and nonionogenic tenside to obtain polymer-nonionogenic tenside matrix material, utilize solvent refluxing extraction or low-temperature bake to remove nonionogenic tenside then, promptly get the mesoporous polymer material, continue carbonization, obtain the meso-porous carbon material of corresponding construction; The polymer that perhaps self-assembly is prepared-direct high temperature cabonization of nonionogenic tenside matrix material obtains meso-porous carbon material.
Among the present invention, nonionogenic tenside is dissolved in the water, obtain clarifying water-surfactant soln, perhaps add a certain amount of organic cosolvent, and then mix with the high-molecular precursor solution that contains acid base catalysator, reaction is 5-24 hour under 30-120 ℃ of temperature, obtains precipitation, obtains product after the filtration; With product reflux extraction in organic solvent, perhaps under the inert atmosphere, template is removed in 350-500 ℃ of roasting carbonization, obtains having the mesoporous polymer of orderly mesoscopic structure; Perhaps with product directly under inert atmosphere 600-1700 ℃ of high temperature cabonization promptly obtain the meso-porous carbon material of high-specific surface area; Perhaps the further carbonization of mesoporous polymer material is promptly obtained the meso-porous carbon material of corresponding construction; The mole proportioning of various reactants is tensio-active agent in the reaction system: polymer presoma: catalyzer: water=1-10 * 10
-2: 0.5-5: 0.2-2: 550,
Wherein the tensio-active agent mass percentage concentration is 2-7%, and polymer presoma mass percentage concentration is 1-4%, reaction PH=1-4 or 8-10.
Among the present invention, the polymer presoma of use can be business-like polymer presoma, or polymer oligopolymer presoma, and their molecular weight are between 200～5000.
Among the present invention, the polymer presoma is resol, polyimide, polypyrrole, polyacrylamide, polyvinylpyridine or polyacrylonitrile.
Among the present invention, used nonionogenic tenside is polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide or alkyl-polyethylene oxide type diblock, triblock copolymer.Used nonionogenic tenside is (as CnH2n+1EOm, EOnPOmEOn, EOnBOmEOn, EOnBOm, EOnPOm etc.), include Brij35 (C12H25EO23), Brij56 (C16H33EO10), Brij78 (C16H33EO20), Brij76 (C18H37EO10), Brij97 (C18H35EO10), P123 (EO20PO70EO20), P103 (EO17PO56EO17), L121 (EO5PO70EO5), P85 (EO26PO39EO26), P65 (EO20PO30EO20), F127 (EO106PO70EO106), F88 (EO100PO39EO100), F98 (EO123PO47EO123), F108 (EO132PO50EO132), B50-6600 (EO39BO47EO39), B70-4600 (EO15BO45EO15), B40-1900 (EO13BO11EO13), B20-3800 (EO34BO11EO34) etc.
Among the present invention, used organic cosolvent is low polarity or nonpolar organic molecule.
Among the present invention, organic cosolvent is C
6-C
10Alkane, dodecane, the tetradecane, n-Hexadecane, whiteruss, toluene, dimethylbenzene or trimethylbenzene.
Among the present invention, used acid is formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; Used organic bases is a methylamine, ethamine, dimethylamine, quadrol, propylamine, urea, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TPAOH, used mineral alkali is an ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta or calcium hydroxide.
Among the present invention, hydrothermal temperature is controlled at 30-90 ℃, obtains post precipitation, 100-120 ℃ of hydrothermal treatment consists in autoclave, perhaps 100-120 ℃ of heat treated in air.
Among the present invention, adopt the solvent refluxing extraction process to remove nonionogenic tenside, used solvent is a sulfuric acid, hydrochloric acid, and nitric acid, sodium hydroxide or potassium hydroxide are at 80-100 ℃ of backflow 20-24h, i.e. degradable tensio-active agent.
Among the present invention, the heat-up rate of roasting, carbonization is 1-5 ℃/minute.
Among the present invention, the aperture of this mesoporous polymer material is 2.0-10.0nm, and pore volume is 0.3-0.9cm
3/ g, specific surface are 300-1000m
2/ g, its space structure is two-dimentional hexagonal structure, is three-dimensional cubic structure, or three-dimensional hexagonal structure.
Among the present invention, the aperture of this meso-porous carbon material is 2.0-7.0nm, and pore volume is 0.3-1.5cm
3/ g, specific surface are 500-2400m
2/ g, its space structure are two-dimentional hexagonal structures, or three-dimensional cubic structure, or three-dimensional hexagonal structure.
In the present invention, for the preparation of mesoporous polymer with some structure and meso-porous carbon material, need to add a certain amount of organic cosolvent, used organic cosolvent can be low polarity or nonpolar organic molecule, as hexane, and heptane, octane, decane, dodecane, the tetradecane, n-Hexadecane, octadecane, whiteruss, toluene, dimethylbenzene, trimethylbenzene etc.
In the present invention, can control the self-assembly of polymer presoma and nonionogenic tenside effectively by the potential of hydrogen of control solution, adjusting obtains the degree of order of mesoporous polymer and meso-porous carbon material.Can control the potential of hydrogen of solution effectively by adding acid or alkali, used acid can be organic acid, as formic acid, and acetate, oxalic acid, propionic acid, phenylformic acid etc. can be mineral acids also, as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.; Used alkali can be organic bases, as methylamine, and ethamine, dimethylamine, diethylamine, propylamine, urea, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH etc. can be mineral alkalis also, as ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta, calcium hydroxide etc.The pH value that is adopted generally is controlled at 8-11, or 1-4.
In the present invention, in reaction process, hydrothermal temperature can be controlled at 30-90 ℃, obtains post precipitation, further 100-120 ℃ of hydrothermal treatment consists in autoclave, perhaps 100-120 ℃ of heat treated in air.
The removal of nonionogenic tenside in the present invention can be adopted the solvent refluxing extraction process, and used solvent can be a sulfuric acid, hydrochloric acid, and nitric acid, sodium hydroxide, potassium hydroxide etc. are at 80-100 ℃ of backflow 24h, i.e. degradable tensio-active agent; Also can adopt the roasting method under inert atmosphere (nitrogen or the argon gas) protection, maturing temperature is 350-500 ℃.
In the present invention, mesoporous polymer can obtain the meso-porous carbon material of corresponding construction by the high temperature cabonization under inert atmosphere (nitrogen or argon gas) protection; Also can polymer-nonionogenic tenside matrix material directly also can be obtained meso-porous carbon material at the indignant high temperature cabonization down of inertia without mesoporous polymer.The roasting carbonization temperature is 350-1400 ℃.Heat-up rate is generally 1-5oC/min.
In the present invention, the aperture that obtains the mesoporous polymer material is 2.0-10.0nm, and pore volume is 0.3-0.9cm
3/ g, specific surface are 300-1000m
2/ g.Its space structure can be two-dimentional hexagonal structure (spacer p6m), also can be that three-dimensional cubic structure is (as spacer Ia-3d, Im-3m), or three-dimensional hexagonal structure (as spacer P63/mmc) etc.The productive rate that obtains mesoporous polymer is 60-95%.Particle size can be at micron order (1-100 μ m), also can be at millimeter level (1-10mm), and pattern can be bar-shaped, and is spherical or fibrous.The color of product can be brown, yellow or black.
In the present invention, the aperture of the mesoporous carbon that obtains is 2.0-7.0nm, and pore volume is 0.3-1.5cm
3/ g, specific surface are 500-2400m
2/ g.Its space structure can be two-dimentional hexagonal structure (spacer p6m), also can be that three-dimensional cubic structure is (as spacer Ia-3d, Im-3m), or three-dimensional hexagonal structure (as spacer P63/mmc) etc.The productive rate that obtains mesoporous carbon is 30-60%.Through after the carbonization, the meso-porous carbon material that obtains keeps original pattern substantially, and particle size can be at micron order (1-50 μ m), also can be at millimeter level (1-5mm), and macro morphology can be bar-shaped, sphere or fiber.
The inventive method is simple, and preparation cost is cheap, and the product specific surface area of acquisition is big, structure height is orderly, and tempting industrial prospect is arranged.
Description of drawings
Fig. 1 is under hydrothermal condition, utilizes the feature XRD figure of mesoporous polymer (a) and mesoporous carbon (b) with two dimension six side p6m structures that novolak resin precursor body and template EO20PO70EO20 assembling prepares.
Fig. 2 is under hydrothermal condition, utilizes the feature nitrogen adsorption-desorption isotherm of mesoporous polymer (a) and mesoporous carbon (b) with two dimension six side p6m structures that novolak resin precursor body and template EO20PO70EO20 assembling prepares.
Fig. 3 is under hydrothermal condition, and (a is b) with mesoporous carbon (c, d) feature TEM figure to utilize the mesoporous polymer with two dimension six side p6m structures that novolak resin precursor body and template EO20PO70EO20 assembling prepares.
Fig. 4 is under hydrothermal condition, utilizes the feature XRD figure of the mesoporous polymer (a) with three-dimensional co-continuous cube Ia-3d structure for preparing of novolak resin precursor body and template EO20PO70EO20 assembling and mesoporous carbon (b).
Fig. 5 is under hydrothermal condition, utilizes the feature nitrogen adsorption-desorption isotherm figure of the mesoporous polymer (a) with three-dimensional co-continuous cube Ia-3d structure for preparing of novolak resin precursor body and template EO20PO70EO20 assembling and mesoporous carbon (b).
Fig. 6 is under hydrothermal condition, and (A is B) with mesoporous carbon (C, D) feature TEM figure to utilize the mesoporous polymer with three-dimensional co-continuous cube Ia-3d structure that novolak resin precursor body and template EO20PO70EO20 assembling prepares.
Fig. 7 is under hydrothermal condition, and the mesoporous polymer with three-dimensional cubic Im-3m structure (a) that utilizes novolak resin precursor body and template EO106PO70EO106 assembling to prepare is composed with the feature XRD figure of mesoporous carbon (b).
Fig. 8 is under hydrothermal condition, utilizes the feature nitrogen adsorption-desorption isotherm of the mesoporous polymer with three-dimensional cubic Im-3m structure (a) for preparing of novolak resin precursor body and template EO106PO70EO106 assembling and mesoporous carbon (b).
Fig. 9 is under hydrothermal condition, and (a, b is c) with mesoporous carbon (d, e, f) feature TEM figure to utilize the mesoporous polymer with three-dimensional cubic Im-3m structure that novolak resin precursor body and template EO106PO70EO106 assembling prepares.
Figure 10 is under hydrothermal condition, and that utilizes that novolak resin precursor body and template EO20PO70EO20 assembling prepares has the two dimension mesoporous polymer of six side p6m structures and an optical photograph of mesoporous carbon.
Figure 11 is under hydrothermal condition, utilizes novolak resin precursor body and the template EO20PO70EO20 mesoporous polymer with three-dimensional co-continuous cube Ia3d structure for preparing of assembling and the optical photograph figure of mesoporous carbon.
Figure 12 is under hydrothermal condition, utilizes the SEM of the mesoporous polymer with three-dimensional cubic Im3m structure for preparing of novolak resin precursor body and template EO106PO70EO106 assembling and mesoporous carbon to scheme.
Embodiment
Embodiment 6, and 5.0g EO106PO70EO106 is dissolved in the 50ml water, mix with the high-molecular precursor solution that obtains in the 59ml example 1, stir 72 hours at 70 ℃, filter, and drying obtains product 3.0g.With product 500 ℃ of roastings 3 hours under nitrogen atmosphere, obtain the mesoporous polymer material, the mesoporous polymer material of gained has three-dimensional cubic Im-3m structure, and the aperture is being 3.0nm, and pore volume is 0.35cm
3/ g, specific surface are 520m
2/ g; 800 ℃ of roastings are 3 hours under nitrogen atmosphere, and the meso-porous carbon material that obtains, the meso-porous carbon material of gained have three-dimensional cubic Im-3m structure, and the aperture is being 2.5nm, and pore volume is 0.55cm
3/ g, specific surface are 1050m
2/ g.
Embodiment 7, and 5.6g EO20PO70EO20 is dissolved in the 50ml water, mix with the high-molecular precursor solution that obtains in the 59ml example 1, stir 72 hours at 70 ℃, filter, and drying obtains product 5.0g.With product 350oC roasting 3 hours under nitrogen atmosphere, obtain the mesoporous polymer material, the mesoporous polymer material of gained has three-dimensional co-continuous cube Ia-3d structure, and the aperture is being 3.3nm, and pore volume is 0.40cm
3/ g, specific surface are 550m
2/ g; 800 ℃ of roastings are 3 hours under nitrogen atmosphere, and the meso-porous carbon material that obtains, the meso-porous carbon material of gained have three-dimensional co-continuous cube Ia-3d structure, and the aperture is being 2.1nm, and pore volume is 0.61cm
3/ g, specific surface are 1100m
2/ g.
Embodiment 8, and 2.8g EO20PO70EO20 is dissolved in the 50ml water, add the 1.4g decane, stir after 12 hours, mix with the high-molecular precursor solution that obtains in the 59ml example 1, stir 72 hours at 70oC, filter, and drying obtains product 5.0g.With product 350 ℃ of roastings 3 hours under nitrogen atmosphere, obtain the mesoporous polymer material, the mesoporous polymer material of proof gained such as XRD spectra has two-dimentional six side space group p6m structures, and the mesoporous polymer material of gained has two dimension six side p6m structures, the aperture is being 5.5nm, and pore volume is 0.55cm
3/ g, specific surface are 560m
2/ g; 800 ℃ of roastings are 3 hours under nitrogen atmosphere, and the meso-porous carbon material that obtains, the meso-porous carbon material of gained have two dimension six side p6m structures, and the aperture is being 3.5nm, and pore volume is 0.60cm
3/ g, specific surface are 1000m
2/ g.
Claims (12)
1. a bigger serface in the aqueous solution, the mesoporous polymer of high-sequential or the preparation method of meso-porous carbon material, it is characterized in that: under hydrothermal condition, utilize organic-organic self-assembly of polymer presoma and nonionogenic tenside to obtain polymer-nonionogenic tenside matrix material, utilize solvent refluxing extraction or low-temperature bake to remove nonionogenic tenside then, promptly get the mesoporous polymer material, continue carbonization, obtain the meso-porous carbon material of corresponding construction; The polymer that perhaps self-assembly is prepared-direct high temperature cabonization of nonionogenic tenside matrix material obtains meso-porous carbon material, concrete steps are: nonionogenic tenside is dissolved in the water, obtain clarifying water-surfactant soln, perhaps add a certain amount of organic cosolvent, and then mix with the high-molecular precursor solution that contains acid base catalysator, reaction is 5-24 hour under 30-120 ℃ of temperature, obtains precipitation, obtains product after the filtration; With product reflux extraction in organic solvent, perhaps under the inert atmosphere, template is removed in 350-500 ℃ of roasting carbonization, obtains having the mesoporous polymer of orderly mesoscopic structure; Perhaps with product directly under inert atmosphere 600-1700 ℃ of high temperature cabonization promptly obtain the meso-porous carbon material of high-specific surface area; Perhaps the further carbonization of mesoporous polymer material is promptly obtained the meso-porous carbon material of corresponding construction; The mole proportioning of various reactants is tensio-active agent in the reaction system: polymer presoma: catalyzer: water=1-10 * 10
-2: 0.5-5: 0.2-2: 550,
Wherein the tensio-active agent mass percentage concentration is 2-7%, and polymer presoma mass percentage concentration is 1-4%, reaction PH=1-4 or 8-10.
2. preparation method according to claim 1 is characterized in that: the polymer presoma of use is business-like polymer presoma, or polymer oligopolymer presoma, and their molecular weight is between 200～5000.
3. preparation method according to claim 2 is characterized in that: the polymer presoma is resol, polyimide, polypyrrole, polyacrylamide, polyvinylpyridine or polyacrylonitrile.
4. preparation method according to claim 1 is characterized in that: used nonionogenic tenside is polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide or alkyl-polyethylene oxide type diblock, triblock copolymer.
5. preparation method according to claim 1 is characterized in that: used organic cosolvent is low polarity or nonpolar organic molecule.
6. preparation method according to claim 5 is characterized in that: organic cosolvent is C
6-C
10Alkane, dodecane, the tetradecane, n-Hexadecane, whiteruss, toluene, dimethylbenzene or trimethylbenzene.
7. preparation method according to claim 1 is characterized in that: used acid is formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; Used organic bases is a methylamine, ethamine, dimethylamine, quadrol, propylamine, urea, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TPAOH, used mineral alkali is an ammoniacal liquor, sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta or calcium hydroxide.
8. preparation method according to claim 1 is characterized in that: hydrothermal temperature is controlled at 30-90 ℃, obtains post precipitation, 100-120 ℃ of hydrothermal treatment consists in autoclave, perhaps 100-120 ℃ of heat treated in air.
9. preparation method according to claim 1 is characterized in that: adopt the solvent refluxing extraction process to remove nonionogenic tenside, used solvent is a sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide or potassium hydroxide, at 80-100 ℃ of backflow 20-24h, i.e. degradable tensio-active agent.
10. preparation method according to claim 1 is characterized in that: the heat-up rate of roasting, carbonization is 1-5 ℃/minute.
11. the mesoporous polymer material that preparation method according to claim 1 obtains, it is characterized in that: the aperture of this mesoporous polymer material is 2.0-10.0nm, and pore volume is 0.3-0.9cm
3/ g, specific surface are 300-1000m
2/ g, its space structure is two-dimentional hexagonal structure, is three-dimensional cubic structure, or three-dimensional hexagonal structure.
12. the meso-porous carbon material that preparation method according to claim 1 obtains, it is characterized in that: the aperture of this meso-porous carbon material is 2.0-7.0nm, and pore volume is 0.3-1.5cm
3/ g, specific surface are 500-2400m
2/ g, its space structure are two-dimentional hexagonal structures, or three-dimensional cubic structure, or three-dimensional hexagonal structure.
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| US8559162B2 (en) | 2009-12-07 | 2013-10-15 | Delta Electronics, Inc. | Mesoporous carbon material, fabrication method thereof and supercapacitor |
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| CN111705683B (en) * | 2020-05-20 | 2021-11-23 | 中国路桥工程有限责任公司 | Dehumidification and corrosion prevention method for main cable of large suspension bridge |
| CN111662092A (en) * | 2020-07-13 | 2020-09-15 | 复旦大学 | Three-dimensional ordered honeycomb cross-linked macroporous carbon and super-assembly preparation method thereof |
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| CN1511785A (en) * | 2002-12-30 | 2004-07-14 | 新加坡纳米材料科技有限公司 | Silicon dioxide mesoporous material and its preparing method |
| CN1696180A (en) * | 2005-04-28 | 2005-11-16 | 复旦大学 | Organic pore-borne material generated by self-assembly of organic and organic, and preparation method |
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