CN102380334A - Mesoporous high polymer or carbon/silicon oxide nano-composite material with three-dimensional pore canal structure and preparation method thereof - Google Patents
Mesoporous high polymer or carbon/silicon oxide nano-composite material with three-dimensional pore canal structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mesoporous high polymer or carbon/silicon oxide nano-composite material with a three-dimensional pore canal structure. The mesoporous high polymer or carbon/silicon oxide nano-composite material is prepared by mixing PDMS-PEO (Polydimethylsiloxane-Poly Ethylene Oxide) and F127 serving as mixed structure directing agents and a phenolic resin performed polymer Resol serving as a carbon source precursor and reacting to obtain an As-made intermediate, and calcining, wherein crystal diffraction peaks of 110, 200, 211, 220, 310, 222 and 321 are shown in the small angle X ray scattering (SAXS) map of the As-made intermediate, and the q value ratio of the diffraction peaks is shown in the specifications. The specific surface area of the mesoporous carbon/silicon oxide nano-composite material with a three-dimensional cubic Imm pore canal structure is 650-1,600m<2>/g, the pore volume range is 0.45-0.63 cm<3>/g, the pore size is 5.0-6.2 nanometers, and the stability of a mesoporous material framework is up to 900 DEG C. The high polymer or carbon/silicon oxide nano-composite material provided by the invention is particularly suitable for the fields of super capacitor electrode materials, adsorbents, catalyst carriers, separation of biomolecules, gas-sensitive materials, optoelectronic devices, hydrogen storage and the like.
Description
Technical field
The present invention relates to the nanometer new material technology field, be specifically related to a kind of three-dimensional cubic Im that has
mMeso-porous nano composite of pore passage structure and preparation method thereof.
Background technology
Ordered mesoporous material is to be template with the surfactant molecule aggregation, and the pore passage structure rule that assembles through the interfacial interaction between organic matter and the inorganic matter, aperture are between the porous material of 2～50 nm.Mesoporous material has following advantageous characteristic feature: 1. long-range promptly is situated between and sees the orderly pore passage structure of horizontal structure; 2. pore-size distribution is narrow, and pore size can be adjustable continuously; 3. through optimizing synthesis condition or carrying out post processing, can have good heat endurance and certain hydrothermal stability; 4. high specific area can be up to 1000 ~ 1500 m
2/ g; 5. particle has regular profile, and can in micro-meter scale, keep the duct order of height; 6. porosity is high; 7. unsaturated group is rich on the surface.Above-mentioned characteristic makes it play an important role at aspects such as absorption, catalysis, separation.In addition, mesoporous material also shows poromerics and unrivaled superiority of large pore material and wide application prospect in fields such as electrode material for super capacitor, novel assembled material, photoelectric device, microelectric technique, chemical sensor, nonlinear optical materials.
The meso-porous nano composite not only has the pliability of organic component, hydrophobic and easy characteristics such as functionalized, also has performances such as high heat endurance of inorganic component and mechanical strength simultaneously.Mesoporous carbon/monox nanometer composite is a kind of important meso-porous nano composite, has better heat, conduction, machinery and chemical property etc. than single mesoporous carbon or meso pore silicon oxide material.Simultaneously, the silica component in the system can effectively overcome the shortcoming that skeleton shrinks seriously in the simple organic system carbonisation, the aperture is little, specific area is low.One of important use of mesoporous carbon/monox nanometer composite is to be used for preparing large aperture, meso-porous carbon material that skeleton stability is high.
At present, the synthetic method of mesoporous carbon/monox nanometer composite mainly contains the functionalisation of surfaces of mesopore silicon oxide, back grafting and ternary assemble method altogether.The functionalisation of surfaces method of mesopore silicon oxide is to utilize to contain the silicon source of organic functional group or the special functionalized mesoporous organic silicon oxide of surfactant synthetic surface; The further method of carbonization then; Silica reagent and surfactant expensive raw material price and be difficult to synthesize in this method are unfavorable for producing in enormous quantities; Back grafting is filled polymer or a carbon in meso pore silicon oxide material, the method for then carrying out carbonization, and this method complex operation, uneconomical, and the very difficult control of polymerization process cause the duct to stop up easily; Ternary construction from part altogether is that the advanced material laboratory Zhao Dongyuan of Fudan University professor seminar took the lead in reporting in 2006; At first assemble synthesising mesoporous macromolecule/monox nanometer composite altogether through the ternary of commercial triblock copolymer, ethyl orthosilicate and phenolic resins performed polymer; Further carry out calcination process and be translated into mesoporous carbon/monox nanometer composite; This method has overcome the shortcoming of preceding two kinds of methods, but adopts this method only can obtain having two dimension six sides
P6mThe mesoporous carbon of structure/monox nanometer composite.And the mesoporous carbon/monox nanometer composite with three-dimensional cubic pore passage structure is not seen bibliographical information so far.
Block copolymer dimethyl silicone polymer-polyoxyethylene (PDMS-PEO) is one of common organic silicon surfactant, do as one likes can difference very big polysiloxanes segment be connected through chemical bond with polyether segment and form.Wherein, Polysiloxanes is siliceous organic compound; The silicone atom special construction that alternately occurs is given its many good performances, like low surface tension, good viscosity temperature characteristic, compliance, in polar surfaces spread property and excellent hydrophobic property be adapted at the serviceability etc. under the wide temperature range; It is water-soluble that hydrophilic polyether segment is given polysiloxanes, makes excellent properties such as its high-low temperature resistant that had both had traditional polysiloxanes, anti-aging, low surface tension, has lubricated, soft, good spreadability and emulsion stability etc. again.In addition, the PDMS-PEO block copolymer also has biocompatibility, good adaptability and low vitrification point, so PDMS-PEO is a kind of in numerous surfactants with advantage.
Up to now; To adopt PDMS-PEO be the rarely seen N. Husing of template poromerics at bibliographical information in 2003; It adopts PDMS-PEO is the synthesizing porous silica material of template; But the document does not characterize the pore structure and the character thereof of gained material, can not confirm that promptly it has orderly meso-hole structure.And; The document adopts not too big meaning of PDMS-PEO synthesizing mesoporous monox material, has only the advantage of its increase skeleton stability of competence exertion and hole diameter enlargement etc. when adopting PDMS-PEO as the synthesising mesoporous carbon of structure directing agent/silicon silica nano composite material or meso-porous carbon material.
Summary of the invention
The object of the invention is to provide a kind of mesoporous polymer or carbon/monox nanometer composite of tool three-dimensional open-framework.
Another object of the present invention is to provide the preparation method of above-mentioned composite.
The objective of the invention is to realize through following technical scheme:
A kind of mesoporous polymer of tool three-dimensional open-framework or carbon/monox nanometer composite; It is characterized in that: it is to adopt bi-block copolymer dimethyl silicone polymer-polyoxyethylene (PDMS-PEO) and triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO; F127) be the mixed structure directed agents; Phenolic resins performed polymer Resol is the carbon source precursor body, mix, react the As-made intermediate, make through roasting again; Said As-made intermediate in its small angle X ray scattering (SAXS) collection of illustrative plates, has 110,200,211,220,310,222 and 321 crystal face diffraction maximums, said diffraction maximum
qValue is than doing
Above-mentioned As-made intermediate, it has the small angle X ray scattering curve shown in a among Fig. 1.
Nitrogen adsorption/the desorption isotherm of the mesoporous polymer of above-mentioned tool three-dimensional open-framework or carbon/monox nanometer composite has IV type nitrogen adsorption curve and H2 type hysteresis loop.
The preparation method of the mesoporous polymer of above-mentioned tool three-dimensional open-framework or carbon/monox nanometer composite; It is characterized in that: with bi-block copolymer dimethyl silicone polymer-polyoxyethylene (PDMS-PEO) and triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO; F127) solution; Mix, dry reaction with phenolic resins performed polymer Resol solution, make the mesoporous polymer or the carbon/monox nanometer composite of tool three-dimensional open-framework again through roasting; Said drying time is 20～30h, and temperature is 80～100 ℃.
The solution of above-mentioned PDMS-PEO and F127 is PDMS-PEO and F127 to be dissolved in the solvent make, and above-mentioned phenolic resins performed polymer solution is the phenolic resins performed polymer to be dissolved in the solvent make; Said solvent can be toluene, absolute ethyl alcohol, THF (oxolane) etc., most preferably adopts THF as solvent.
Above-mentioned PDMS-PEO block copolymer is one type important in the organosilicon material, and its molecular structure model is as follows:
The molecular structure of PDMS-PEO
Can find out that silicon atom is in the tetrahedron center in compound, two methyl are perpendicular on silicon and the plane that two adjacent oxygen atoms are connected; Because Si-C key bond distance is bigger, to such an extent as to three hydrogen on two nonpolar methyl just as the umbrella that struts, thereby make it have good hydrophobicity.PDMS-PEO molecular weight of the present invention is 3000 ~ 15000, can be PDMS-PEO (
M w=3012, DMS
32-EO
20), PDMS-PEO (
M w=5660, DMS
60-EO
40), PDMS-PEO (
M w=8490, DMS
90-EO
60); More than be the commercially available prod.
PEO-PPOX of the present invention-PEO (PEO-PPO-PEO), its
M w=12600, EO
106-PO
70-EO
106, trade name F127, block copolymer are one type of non-ionic (polymeric surfactant)s, and title is Pluronic (BASF AG), is the commercially available prod, and its structure is following:
M and n are respectively the chain link number of EO and PO segment.
Above-mentioned carbon source precursor phenolic resins performed polymer Resol, molecular weight is 400<
M w <500, its cross-linked network is following:
The phenolic resins structural representation
Above-mentioned roasting preferably, obtains three-dimensional order mesoporous polymer/monox nanometer composite at 300 ~ 450 ℃ of roasting 2 ~ 4 h, and roasting 1.5 ~ 3 h obtain three-dimensional order mesoporous carbon/monox nanometer composite in 800 ~ 950 ℃ of temperature ranges.
Further preferably, above-mentioned PDMS-PEO's
M w=3012, DMS
32-EO
20
Further preferably, the mass percentage concentration of the THF solution of above-mentioned phenolic resins performed polymer is 15 ~ 40wt%, is preferably 20wt%; In the oxolane of said PDMS-PEO and F127 (THF) solution, the mass percentage concentration of PDMS-PEO and F127 is 3 ~ 7 wt%, is preferably 5wt%.
The mass ratio of above-mentioned template PDMS-PEO, F127 and carbon source precursor body Resol is 0.7 ~ 1.2:0.7 ~ 1.2:1.8 ~ 2.2, is preferably 1:1:2.
Specifically, the preparation method of the mesoporous polymer of tool three-dimensional open-framework or carbon/monox nanometer composite, carry out as follows:
(1). F127 and PDMS-PEO are dissolved in the oxolane (THF), add the THF solution of phenolic resins performed polymer Resol then, stir 0.3 ~ 0.7 h and obtain uniform solution; Wherein the mass ratio of material is PDMS-PEO:F127:Resol=1:1:2; The mass percentage concentration of the THF solution of phenolic resins performed polymer is 15 ~ 40wt%, and in the THF solution of PDMS-PEO and F127, PDMS-PEO and F127 mass percentage concentration are 3 ~ 7 wt%; Said solution is transferred in the culture dish, and 5～8 h that volatilize under the room temperature place 100 ℃ of baking oven internal reaction 24h with culture dish again, obtain transparent orange-yellow thin-film material, and above-mentioned material is scraped from culture dish, and grind into powder obtains the As-made intermediate;
(2). place tube furnace under the nitrogen gas protection, to carry out roasting in said As-made sample; 300 ~ 450 ℃ of roasting 2 ~ 4h obtain three-dimensional order mesoporous polymer/monox nanometer composite, and roasting 1.5 ~ 3 h obtain three-dimensional order mesoporous carbon/monox nanometer composite in 800 ~ 950 ℃ of temperature ranges; In the process of roasting, when temperature is below 600 ℃ the time, programming rate is set at 1 ℃/min, and when temperature is more than 600 ℃ the time, programming rate is set at 5 ℃/min.
More particularly, the preparation method of the mesoporous polymer of above-mentioned tool three-dimensional open-framework or carbon/monox nanometer composite:
(1). 1.0 g F127 and 1.0 g PDMS-PEO are dissolved among the 40.0 g THF, and 40 ℃ are stirred 10 min, obtain the solution of transparent and homogeneous.Add then 10.0 g, 20 wt % phenolic resins performed polymers (
M w<500) THF solution stirs 0.5h and obtains uniform solution.Above-mentioned solution is transferred in the culture dish, and 5～8 h that volatilize under the room temperature place 24h in 100 ℃ of baking ovens with culture dish again, obtain transparent orange-yellow thin-film material.Above-mentioned material is scraped from culture dish, and grind into powder obtains the As-made intermediate;
(2). place tube furnace under the nitrogen gas protection, to carry out roasting in the As-made sample; 400 ℃ of roasting 3h obtain three-dimensional order mesoporous polymer/monox nanometer composite, obtain three-dimensional order mesoporous carbon/monox nanometer composite at 900 ℃ of roasting 2h; In the process of roasting, when temperature is below 600 ℃ the time, programming rate is set at 1 ℃/min, and when temperature is more than 600 ℃ the time, programming rate is set at 5 ℃/min.
The present invention has following beneficial effect:
1, the present invention has three-dimensional cubic
Im 
mThe specific area of the mesoporous carbon of pore passage structure/monox nanometer composite is at 650 ~ 1600 m
2In/g the scope, the pore volume scope is 0.45 ~ 0.63 cm
3/ g, aperture size is in 5.0 ~ 6.2 nm scopes, and the mesoporous material skeleton stability is up to 900 ℃.Macromolecule of the present invention or carbon/monox nanometer composite is specially adapted to the fields such as separation, gas sensitive, opto-electronic device and Chu Qing of electrode material for super capacitor, adsorbent, catalyst carrier, biomolecule.
2, the hydrophobicity of PDMS segment is very strong in the PDMS-PEO block copolymer that adopts in the preparation of meso-porous nano composite of the present invention; The inventive method has made full use of this characteristic; Itself and triblock copolymer F127 carry out when composite; Obviously increased the hydrophobic inner core of F127, thereby effectively increased the aperture of the mesoporous carbon/monox nanometer composite that makes, increased in 5.0 ~ 6.2 nm scopes from 3 ~ 4 nm in traditional meso-porous carbon material aperture.On the other hand; PDMS-PEO again can be as the silicon source; Prepared material is in high-temperature roasting template agent removing process; Inorganic PDMS segment is converted into the silica component, thereby can silica be incorporated in the meso-porous carbon material system through one-step method, need not introduce expensive silane reagent; And avoided traditional sol-gel process; Simplified the preparation process of mesoporous polymer or carbon/monox nanometer composite greatly, thereby hewed out a novel economical rationality, workable mesoporous polymer or the synthetic route of carbon/monox nanometer composite, this simple one-step method is that mass preparation mesoporous polymer or carbon/monox nanometer composite provide effective way.
Description of drawings
Fig. 1 is small angle X ray scattering (SAXS) collection of illustrative plates of three-dimensional order meso-porous nano composite: (a) As-made intermediate; (b) the three-dimensional order meso-porous nano composite (MP-CS-400N) that obtains of the following 400 ℃ of roastings of nitrogen atmosphere; (c) the three-dimensional order meso-porous nano composite (MP-CS-900N) that obtains of the following 900 ℃ of roastings of nitrogen atmosphere;
Fig. 2 be three-dimensional order meso-porous nano composite MP-CS-400N (a, b, c) and MP-CS-900N (d, e, f) along [100] (a, d), [110] (b, e) and [111] (illustration is the fourier diffraction collection of illustrative plates for c, f) the TEM image of direction;
Fig. 3 is the nitrogen adsorption/desorption isotherm (A) and the pore size distribution curve (B) of three-dimensional order meso-porous nano composite: (a) sample of 400 ℃ of nitrogen atmosphere roastings (MP-CS-400N); (b) sample of 900 ℃ of nitrogen atmosphere roastings (MP-CS-900N), nitrogen adsorption/desorption isotherm a and b have moved 300 and 200 cm respectively vertically upward
3STP/g.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is further specified; But following explanation is not to limit of the present invention; Any to distortion of the present invention and change, only otherwise break away from spirit of the present invention, all should belong to the defined scope of accompanying claims of the present invention.
Embodiment 1Synthesizing of phenolic resins performed polymer
With 0.61g phenol in 40～42 ℃ of fusions; Under this temperature, add 0.13 g, the 20 wt % NaOH aqueous solution and stir 10 min; Add 1.05 g 37wt % formalins, be warming up to 70～75 ℃ of reaction 1h, reduce to room temperature; Using the pH value of 0.6mol/L HCl solution regulator solution is 7.0, is lower than 50 ℃ of vacuum decompression dehydration 1～2h.The thick liquid that obtains is dissolved in is made into 20 wt% solution for later use among the THF.
Embodiment 2The preparation of As-made sample
1.0 g F127 and 1.0 g PDMS-PEO are dissolved in the 40.0 g oxolanes (THF), and 40 ℃ are stirred 10 min, obtain the solution of transparent and homogeneous.Add then the above-mentioned 20 wt % phenolic resins performed polymers that make of 10.0 g (
M w<500) THF solution stirs 0.5h and obtains uniform solution.Above-mentioned solution is transferred in the culture dish, and 5～8 h that volatilize under the room temperature place 24h in 100 ℃ of baking ovens with culture dish again, obtain transparent orange-yellow thin-film material.Above-mentioned material is scraped from culture dish, and grind into powder obtains the As-made intermediate.
Triblock copolymer F127 among this embodiment (
M w=12600, EO
106-PO
70-EO
106) purchase company in Aldrich, PDMS-PEO (
M w=3012, DMS
32-EO
20) purchase Mai Ruier chemical technology Co., Ltd in Shenzhen, other reagent is purchased the chemical reagents corporation in Shanghai, does not all further handle before all reagent use.
Embodiment 3The preparation of three-dimensional order mesoporous polymer/silica, carbon/monox nanometer composite
Place tube furnace under the nitrogen gas protection, to carry out roasting in above-mentioned As-made intermediate; 400 ℃ of roasting 3h obtain three-dimensional order mesoporous polymer/monox nanometer composite, obtain three-dimensional order mesoporous carbon/monox nanometer composite at 900 ℃ of roasting 2h; In the process of roasting, when temperature is below 600 ℃ the time, programming rate is set at 1 ℃/min, and when temperature is more than 600 ℃ the time, programming rate is set at 5 ℃/min.The identified as samples of roasting gained is designated as MP-CS-400N under 400 ℃ of nitrogen atmospheres, and the identified as samples of roasting gained is designated as MP-CS-900N under 900 ℃ of nitrogen atmospheres.
Adjustment in the present invention such as each material variety and usage ratio, technological parameter, situation such as the meso-porous nano composite degree of order difference of prepared three-dimensional order pore passage structure, skeleton contraction are different.
Embodiment 4Adopt the German Brooker Nanostar U of company small angle X ray scattering appearance (CuK α) to measure above-mentioned gained sample is carried out small angle X ray scattering (SAXS) mensuration, pipe is pressed 40 kV, pipe stream 35 mA, and be 30 min writing time.Gained SAXS is as shown in Figure 1.The SAXS spectrogram that can be found out the As-made sample by Fig. 1 is at 0.46,0.63 and 0.80 nm
-13 diffraction maximums clearly appear in the place.In addition, exist
qValue is 0.92,1.00,1.13 and 1.19 nm
-14 diffraction maximums also appear.These seven diffraction maximums
qValue is than doing
, therefore quilt is pointed out and is body-centered cubic
Imm110,200,211,220,310,222,321 crystal face diffraction maximums.The cell parameter of being calculated As-made sample and MP-CS-400N by the SAXS spectrogram is respectively 19.3 and 16.9 nm, and the skeleton shrinkage factor is 12%.Further the temperature with roasting is increased to 900 ℃, the peak position of the SAXS spectrogram diffraction maximum of gained material MP-CS-900N to
qThe direction that value increases moves, and the cell parameter of calculating is 13.5 nm, is illustrated in that skeleton further shrinks in the roasting process.
Embodiment 5Adopt Japanese JEOL JEM2011 type high-resolution-ration transmission electric-lens (TEM) that the structure of above-mentioned gained material is characterized, accelerating potential is 200 kV.The preparation process of sample is following: pulverous material dissolves is formed in ethanol dissolve the slurry attitude, use the copper mesh that has carbon film to hang and get this molten slurry, can directly be used for after the drying observing.The gained result is as shown in Figure 2.Can find out that along [100], the TEM image of [110] and [111] direction has shown large-area ordered structure to As made intermediate, proves that further the structure of gained has orderly body-centered cubic after 400 ℃ and 900 ℃ of roastings
ImmStructure.This shows that the introducing of PDMS-PEO copolymer does not reduce the order of meso-hole structure, but under its guiding, forms orderly meso-hole structure.
Embodiment 6Adopt Micromeritics Tristar 3000 absorption appearance that above-mentioned gained sample is carried out nitrogen adsorption/desorption performance test.Nitrogen adsorption/desorption isotherm obtains under 77 K conditions.Before the test, sample is no less than 6 h in 200 ℃ of degassings in advance under vacuum condition.The specific area of sample (
S BET ) adopt the BET method, calculate according to relative pressure adsorpting data in the 0.04-0.2 scope; Pore volume (
V t) and the aperture (
D) adopt the BJH Model Calculation by thermoisopleth absorption branch, wherein pore volume is used relative pressure
P/
P 0The adsorbance at=0.992 place is calculated.Nitrogen adsorption/the desorption isotherm (A) and the pore size distribution curve (B) of gained meso-porous nano composite are as shown in Figure 3.Can be found out that by figure the mesoporous material MP-CS-400N that 400 ℃ of roastings obtain under nitrogen atmosphere has IV type nitrogen adsorption curve and H2 type hysteresis loop, this is the adsorpting characteristic that typically has the mesoporous material of three-dimensional cage shape pore passage structure, at relative pressure
P/P 0 In=0.6-0.7 the scope, its adsorption curve has an obvious hop that is caused by the capillary condensation phenomenon, explains that this material has very narrow pore-size distribution.The specific area of MP-CS-400N, pore volume and aperture are respectively 873 m
2/ g, 0.47 cm
3/ g and 8.0 nm, its average pore size is greater than the aperture (3.9 nm) of C-FDU-16.This shows that the introducing of PDMS-PEO has obviously reduced the skeleton contraction and increased the aperture.The adsorption curve of the mesoporous material MP-CS-900N that 900 ℃ of roastings obtain and MP-CS-400N's is similar; Difference is that the tangible capillary condensation phenomenon of MP-CS-900N occurs in the area of low pressure; Corresponding to the corresponding minimizing (5.4 nm) in aperture, but the BET specific area of MP-CS-900N is 1410 m
2/ g much larger than the specific area of MP-CS-400N, shows to have produced microcellular structure.
Claims (10)
1. the mesoporous polymer of a tool three-dimensional open-framework or carbon/monox nanometer composite; It is characterized in that: it is to adopt bi-block copolymer dimethyl silicone polymer-polyoxyethylene (PDMS-PEO) and triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO; F127) be the mixed structure directed agents; Phenolic resins performed polymer Resol is the carbon source precursor body, mix, react the As-made intermediate, make through roasting again; Said As-made intermediate in its small angle X ray scattering (SAXS) collection of illustrative plates, has 110,200,211,220,310,222 and 321 crystal face diffraction maximums, said diffraction maximum
qValue is than doing
2. nano composite material as claimed in claim 1 is characterized in that: said As-made intermediate, it has the small angle X ray scattering curve shown in a among Fig. 1.
3. according to claim 1 or claim 2 nano composite material, it is characterized in that: the nitrogen adsorption/desorption isotherm of the mesoporous polymer of said tool three-dimensional open-framework or carbon/monox nanometer composite has IV type nitrogen adsorption curve and H2 type hysteresis loop.
4. like the preparation method of each said nano composite material of claim 1～4; It is characterized in that: with bi-block copolymer dimethyl silicone polymer-polyoxyethylene (PDMS-PEO) and triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO; F127) oxolane (THF) solution; Mix with oxolane (THF) solution of phenolic resins performed polymer Resol, oven dry reacts, and makes the mesoporous polymer or the carbon/monox nanometer composite of tool three-dimensional open-framework again through roasting; Said drying time is 20～30h, and temperature is 80～100 ℃.
5. preparation method as claimed in claim 4; It is characterized in that: said roasting; Obtain three-dimensional order mesoporous polymer/monox nanometer composite at 300 ~ 450 ℃ of roasting 2 ~ 4h, roasting 1.5 ~ 3 h obtain three-dimensional order mesoporous carbon/monox nanometer composite in 800 ~ 950 ℃ of temperature ranges.
6. like claim 4 or 5 described preparation methods, it is characterized in that: said PDMS-PEO's
M w=3012, DMS
32-EO
20
7. like claim 4,5 or 6 described preparation methods, it is characterized in that: the mass percentage concentration of the THF solution of said phenolic resins performed polymer is 15 ~ 40wt%; In the oxolane of said PDMS-PEO and F127 (THF) solution, the mass percentage concentration of PDMS-PEO and F127 is 3 ~ 7 wt%.
8. preparation method as claimed in claim 7; It is characterized in that: the mass percentage concentration of the THF solution of said phenolic resins performed polymer is 20wt%; In the oxolane of said PDMS-PEO and F127 (THF) solution, the mass percentage concentration of PDMS-PEO and F127 is 5wt%.
9. like each described preparation method of claim 4～8, it is characterized in that: the mass ratio of said template PDMS-PEO, F127 and carbon source precursor body Resol is 0.7 ~ 1.2:0.7 ~ 1.2:1.8 ~ 2.2.
10. preparation method as claimed in claim 4, carry out as follows:
F127 and PDMS-PEO are dissolved in the oxolane (THF), add the THF solution of phenolic resins performed polymer Resol then, stir 0.3 ~ 0.7 h and obtain uniform solution; Wherein the mass ratio of material is PDMS-PEO:F127:Resol=1:1:2; The mass percentage concentration of the THF solution of phenolic resins performed polymer is 15 ~ 40wt%, and in the THF solution of PDMS-PEO and F127, PDMS-PEO and F127 mass percentage concentration are 3 ~ 7 wt%wt%; Said solution is transferred in the culture dish, and 5～8 h that volatilize under the room temperature place 100 ℃ of baking oven internal reaction 24h with culture dish again, obtain transparent orange-yellow thin-film material, and above-mentioned material is scraped from culture dish, and grind into powder obtains the As-made intermediate;
Place tube furnace under the nitrogen gas protection, to carry out roasting in said As-made sample; 300 ~ 450 ℃ of roasting 2 ~ 4h obtain three-dimensional order mesoporous polymer/monox nanometer composite, and roasting 1.5 ~ 3 h obtain three-dimensional order mesoporous carbon/monox nanometer composite in 800 ~ 950 ℃ of temperature ranges; In the process of roasting, when temperature is below 600 ℃ the time, programming rate is set at 1 ℃/min, and when temperature is more than 600 ℃ the time, programming rate is set at 5 ℃/min.
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| CN111729517A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Asymmetric composite membrane based on ordered mesoporous carbon, super-assembly preparation method and application thereof |
| CN112259910A (en) * | 2020-09-27 | 2021-01-22 | 北京理工大学 | Cubic hole carbon coating diaphragm of lithium metal battery and preparation method thereof |
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| CN110650754A (en) * | 2017-03-29 | 2020-01-03 | 阿托斯有限责任公司 | Carrier composition for bone substitute material |
| CN109874089A (en) * | 2019-01-25 | 2019-06-11 | 歌尔股份有限公司 | Aerosil sound-absorbing material and sounding device |
| CN111729517A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Asymmetric composite membrane based on ordered mesoporous carbon, super-assembly preparation method and application thereof |
| CN112259910A (en) * | 2020-09-27 | 2021-01-22 | 北京理工大学 | Cubic hole carbon coating diaphragm of lithium metal battery and preparation method thereof |
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