CN102642843B - Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material - Google Patents
Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material Download PDFInfo
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Abstract
The invention relates to a method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and a carbon nano material, belonging to the field of mesoporous nano material preparation. The method comprises the following steps: mixing water and alcohols to prepare a reaction solvent; adding a catalyst alkali, a reaction reagent resorcin and a surfactant CTAB (cetyltrimethylammonium bromide) into the reaction solvent; after stirring, adding a reaction reagent formaldehyde solution and TEOS (tetraethyl orthosilicate) to obtain a mixed solution; continuing stirring the mixed solution at room temperature, removing the supernatant to obtain a precipitate, and drying to obtain solid powder; calcining the solid powder at high temperature under inert gas shielding to carbonize the solid powder, thereby obtaining black solid powder; soaking the black solid powder in a hydrogen fluoride water solution or strongly alkaline solution to remove silicon dioxide, thereby obtaining a multilevel-structure mesoporous carbon material; and calcining the solid powder or black solid powder at high temperature in the air to obtain the multilevel-structure mesoporous silicon dioxide material. The method provided by the invention is simple to operate, has the advantage of low cost, and can implement large-scale production.
Description
Technical field
The present invention relates to a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial.Belong to meso-porous nano field of material preparation.
Background technology
Since 20th century, found the superiority of natural porous material the forties, people just start synthetic porous material section.Pure and (the International Union of Pure and Applied Chemistry of applied chemistry federation according to the world, IUPAC) definition, porous material can be divided into poromerics, mesoporous material and large pore material, and aperture is mesoporous between the hole of 2～50nm.Within 1992, MOBIL company is used alkyl quaternary ammonium salts type cats product successfully to synthesize M41S mesoporous material (MCM-41, MCM-48, MCM-50) as template first, thereby porous material is expanded to mesoporous from micropore, and between poromerics (as zeolite) and large pore material (as activated carbon), erected seat bridge fine strain of millet.
Mesoporous material, as silicon-dioxide and carbon material, due to its large specific surface area and pore volume, good thermostability and certain hydrothermal stability, and modifiable surface properties, regulatable macroscopic form and without plurality of advantages such as physiology toxicity, in research fields such as heterogeneous catalyst, absorption and chromatographic separation, chemical sensor, biomedicine and high inorganic materials, all show the incomparable superiority of traditional inorganic porous material and wide application prospect.
In recent years, a lot of excellent properties that have due to multilevel hierarchy micro Nano material, the micro Nano material that design and preparation have a multilevel hierarchy has obtained the attention of Many researchers.Up to the present, some mesoporous silicon oxide and carbon materials with peculiar multilevel hierarchy are in the news, for example hollow Mesoporous Spheres, the microballoon with multi-layer mesoporous shell structure, the structure mesoporous ball of eggshell-yolk, multistage meso-hole structure microballoon, and other non-spherical multilevel hierarchies.Because these materials possess every advantage of mesoporous material simultaneously, and be widely used in medicament transport, bio-imaging, water treatment, support of the catalyst, a lot of aspects such as hard template and electrode materials.
Multilevel hierarchy Metaporous silicon dioxide material is generally prepared by the method for hard template and soft template, yet the common step of the method for hard template is more, more loaded down with trivial details time-consuming (J.Mater.Chem., 2011,21,5290.; Adv.Mater., 2010,22,838.; J.Phys.Chem.G, 2011,115,17717.), and the common pattern heterogeneity of the resulting material of the method for soft template (Chem.Commun., 2008,2629.; J.Am.Chem.Soc., 2007,129,14576.; J.Am.Chem.Soc., 2010,132,15144.).For the meso-porous carbon material of multilevel hierarchy, current preparation method also rests on the method for hard template substantially, and other simple preparation methods that comprise soft template are rare report also.In addition, traditional preparation method once can only prepare a kind of material, and this material has single specific pattern, for example mesoporous material of hollow ball shape or tubulose.Therefore, invent a kind of simply, effectively can prepare in large quantities the method for multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial, the application for this class material, has very important significance.
Summary of the invention
The object of the invention is in order to solve in existing multilevel hierarchy mesoporous material technology of preparation method steps more, more loaded down with trivial details time-consuming, and the problem that once can only prepare a kind of material, provides a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial.
The object of the invention is to be achieved through the following technical solutions.
A method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial, comprises the steps:
Step 1: preparation feedback solution
Water and alcohols are hybridly prepared into reaction solvent; In reaction solvent, add catalyzer alkali, reaction reagent Resorcinol and tensio-active agent cetyl trimethylammonium bromide (CTAB); After at room temperature stirring, add reaction reagent formaldehyde solution and tetraethoxysilane (TEOS), obtain mixing solutions; Wherein Resorcinol can generate polymkeric substance resol after reacting with formaldehyde solution, and tetraethoxysilane (TEOS) is hydrolyzed into silicon-dioxide;
Step 2: the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
The mixing solutions that step 1 is made at room temperature continues to stir, and then mixing solutions is transferred in the reaction vessel of sealing and is carried out after hydrothermal treatment consists, removes supernatant liquid and is precipitated thing, obtains pressed powder after dry; Gained pressed powder is the complex body of polymkeric substance resol, silicon-dioxide and tensio-active agent (CTAB).
Step 3: high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
The pressed powder that step 2 is obtained high-temperature calcination under protection of inert gas makes its carbonization, obtains black solid powder, is the complex body of carbon material and silicon-dioxide.
Step 4: the making of multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial
The black solid powder that step 3 is obtained soaks with aqueous hydrogen fluoride solution or strong base solution, removes silicon-dioxide, obtains multilevel hierarchy meso-porous carbon material.
The high-temperature calcination in air of the black solid powder of the pressed powder of step 2 gained or step 3 gained is obtained to multilevel hierarchy Metaporous silicon dioxide material.
The alcohols that alcohols described in step 1 is less than 5 for all carbonatomss, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, primary isoamyl alcohol etc., are preferably ethanol.
Water and alcohols described in step 1 are hybridly prepared into reaction solvent, and wherein the volume ratio of alcohols and water is 4: 3～4: 52.
Catalyzer alkali described in step 1 is that all can ionize the reagent that produces hydroxide ion in water, as sodium hydroxide, and ammonia soln etc.
After catalyzer alkali described in step 1 adds, the mass concentration of alkali reagent in water and alcohols reaction solvent is 0.8～8g/L.
After Resorcinol described in step 1 adds, its mass concentration in water and alcohols reaction solvent is not more than 3%.
After CTAB described in step 1 adds, its mass concentration in water and alcohols reaction solvent is not more than 3%.
The mass concentration of the formaldehyde solution described in step 1 is not less than 30%, and adding the mol ratio of Resorcinol and formaldehyde after formaldehyde solution is 1: 1.2～1: 2.5.
The volume ratio of the add-on of the TEOS described in step 1 and water and alcohols reaction solvent can be 0.25: 28～and 3: 28, be preferably 0.5: 28～2: 28.
The temperature of the hydrothermal treatment consists described in step 2 is 50～200 ℃, is preferably 60～120 ℃.
Rare gas element described in step 3 can be any gas except oxygen or the mixed gas of oxygen-free gas.Be preferably nitrogen, argon gas.
The condition of the high-temperature calcination described in step 3, step 4 is that temperature is not less than 300 ℃.Temperature is preferably 400～1500 ℃,
In aqueous hydrogen fluoride solution described in step 4 or strong base solution, contained solute massfraction is preferably 5wt%～20wt%.
Beneficial effect
1, a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial of the present invention, simple to operate, cost is lower, can realize scale operation.
2, the invention provides a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial, by regulating the proportioning of water and alcohols reaction solvent can obtain mesoporous silicon oxide and the carbon nanomaterial of different-shape and structure.
3, the prepared material of the present invention can be used to environment, biology, catalysis, sensor, the various fields such as optics and electricity.
Accompanying drawing explanation
Fig. 1 is preparation method's of the present invention schematic flow sheet;
Fig. 2 is tubular, hollow mesoporous silicon oxide prepared in embodiment 1 and scanning electron microscope (SEM) figure and transmission electron microscope (TEM) figure of carbon nanomaterial;
Fig. 3 is hollow mesoporous silicon dioxide micro-sphere prepared in embodiment 2 and SEM figure and the TEM figure of eggshell-yolk structure (Rattle-type) mesoporous carbon Nano microsphere;
Fig. 4 is radiation mesoporous silicon dioxide micro-sphere prepared in embodiment 3 and SEM figure and the TEM figure of hollow mesoporous carbon Nano microsphere.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1
Utilize preparation system of the present invention to prepare tubular, hollow mesoporous silicon oxide and carbon nanomaterial
One, preparation feedback solution
1,, in reaction vessel, 4mL ethanol and 24mL water are hybridly prepared into reaction solvent; To adding 0.2mL mass concentration in reaction solvent, be 25%～30% ammonia soln, 0.2g Resorcinol and 0.2gCTAB.
2, above-mentioned mixed solution is at room temperature stirred to 30min, add 0.28mL formaldehyde solution and 1mL TEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
The mixing solutions that step 1 is made at room temperature continues to stir 24h, then mixing solutions is transferred in the reaction vessel of sealing to hydrothermal treatment consists 24h at 100 C temperature, then removes supernatant liquid and is precipitated thing, obtains pressed powder after dry; Gained pressed powder is the complex body of polymkeric substance resol, silicon-dioxide and tensio-active agent (CTAB).
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
The pressed powder that step 2 is obtained 600 C high-temperature calcination 4h under nitrogen protection make its carbonization, obtain black solid powder.Gained black solid powder is the complex body of carbon material and silicon-dioxide.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, the black solid powder of the pressed powder of step 2 gained or step 3 gained 600 C high-temperature calcination 6h in air are obtained to tubular, hollow mesopore silicon dioxide nano material.In accompanying drawing 2, (a) be its SEM figure, (b, c) is its TEM figure.
2, the aqueous hydrogen fluoride solution that black solid powder step 3 being obtained is 10% by mass concentration or strong base solution soak, and remove silicon-dioxide, obtain tubular, hollow mesoporous carbon nano material.In Fig. 2, (d) be its SEM figure, (e, f) is its TEM figure.
Embodiment 2
Utilize preparation system of the present invention to prepare hollow mesoporous silicon dioxide micro-sphere and eggshell-yolk structure (Rattle-type) mesoporous carbon Nano microsphere
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1, difference is 8mL ethanol and 20mL water to be hybridly prepared into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1,, with 1 of the step 4 of embodiment 1, what difference was to obtain is hollow mesoporous silicon dioxide micro-sphere.In accompanying drawing 3, (a) be its SEM figure, (b, c) is its TEM figure.
2,, with 2 of the step 4 of embodiment 1, what difference was to obtain is eggshell-yolk structure (Rattle-type) mesoporous carbon Nano microsphere.In accompanying drawing 3, (d) be its SEM figure, (e, f) is its TEM figure.
Embodiment 3
Utilize preparation system of the present invention to prepare radiation mesoporous silicon dioxide micro-sphere and hollow mesoporous carbon Nano microsphere.
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1, difference is 12mL ethanol and 16mL water to be hybridly prepared into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1,, with 1 of the step 4 of embodiment 1, what difference was to obtain is radiation mesoporous silicon dioxide micro-sphere.In accompanying drawing 4, (a) be its SEM figure, (b, c) is its TEM figure.
2,, with 2 of the step 4 of embodiment 1, what difference was to obtain is hollow mesoporous carbon Nano microsphere.In accompanying drawing 4, (d) be its SEM figure, (e, f) is its TEM figure.
Embodiment 4
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1, difference is 4mL Virahol and 24mL water to be mixedly configured into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 5
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1, difference is 4mL primary isoamyl alcohol and 24mL water to be mixedly configured into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 6
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.2g Resorcinol and 0.2g CTAB that difference is to add 1mL mass concentration in reaction solvent.
2, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Two, the preparation of superpolymer/silicon-dioxide/tensio-active agent complex body
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 7
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.2g Resorcinol and 0.2g CTAB that difference is to add 0.1mL mass concentration in reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 8
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 10% sodium hydroxide solution, 0.2g Resorcinol and 0.2g CTAB that difference is to add 0.5mL mass concentration in reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 9
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.Difference is to add 0.36mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 10
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.Difference is to add 0.16mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 11
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.05g Resorcinol and 0.2g CTAB that difference is to add 0.2mL mass concentration in reaction solvent.
2, with 2 of the step 1 of embodiment 1.Difference is to add 0.14mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 12
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.8g Resorcinol and 0.2g CTAB that difference is to add 0.2mL mass concentration.
2, with 2 of the step 1 of embodiment 1.Difference is to add 1.12mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 13
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.2g Resorcinol and 0.1g CTAB that difference is to add 0.2mL mass concentration.
2, with 2 of the step 1 of embodiment 1.Difference is to add 1.12mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 14
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.2g Resorcinol and 0.5g CTAB that difference is to add 0.2mL mass concentration.
2, with 2 of the step 1 of embodiment 1.Difference is to add 1.12mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 15
One, preparation feedback solution
1,, with 1 of the step 1 of embodiment 1, it is 25%～30% ammonia soln, 0.2g Resorcinol and 0.8g CTAB that difference is to add 0.2mL mass concentration.
2, with 2 of the step 1 of embodiment 1.Difference is to add 1.12mL formaldehyde solution and 1mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 16
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.Difference is to add 0.28mL formaldehyde solution and 0.5mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 17
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.Difference is to add 0.28mL formaldehyde solution and 2mLTEOS.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 18
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.Difference is then mixing solutions to be transferred in the reaction vessel of sealing hydrothermal treatment consists 24h at 60 C temperature
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 19
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.Difference is then mixing solutions to be transferred in the reaction vessel of sealing hydrothermal treatment consists 24h at 120 C temperature
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 20
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 600 C high-temperature calcination 4h under argon shield that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 21
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 600 C high-temperature calcination 4h under the protection of nitrogen hydrogen gas mixture that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 22
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 300 C high-temperature calcination 4h under nitrogen protection that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 23
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 1500 C high-temperature calcination 4h under nitrogen protection that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 24
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 600 C high-temperature calcination 3h under nitrogen protection that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 25
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.Difference is that pressed powder 600 C high-temperature calcination 12h under nitrogen protection that step 2 is obtained make its carbonization.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.
Embodiment 26
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.The aqueous hydrogen fluoride solution that the black solid powder that difference is the step 3 to obtain is 5% by mass concentration or strong base solution soak.
Embodiment 27
One, preparation feedback solution
1, with 1 of the step 1 of embodiment 1.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
Step 2 with embodiment 1.
Three, high temperature cabonization obtains the complex body of carbon material and silicon-dioxide.
Step 3 with embodiment 1.
Four, multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial makes
1, with 1 of the step 4 of embodiment 1.
2, with 2 of the step 4 of embodiment 1.Difference is that aqueous hydrogen fluoride solution or strong base solution that black solid powder that step 3 obtains is 20% by mass concentration soak.
Above-described specific descriptions; object, technical scheme and beneficial effect to invention further describe; institute is understood that; the foregoing is only specific embodiments of the invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. prepare a method for multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously, it is characterized in that: comprise the steps:
Step 1: preparation feedback solution
Water and alcohols are hybridly prepared into reaction solvent; In reaction solvent, add catalyzer alkali, reaction reagent Resorcinol and tensio-active agent cetyl trimethylammonium bromide; After at room temperature stirring, add reaction reagent formaldehyde solution and tetraethoxysilane, obtain mixing solutions; Wherein Resorcinol can generate polymkeric substance resol after reacting with formaldehyde solution, and tetraethoxysilane is hydrolyzed into silicon-dioxide;
Step 2: the complex body of preparing polymkeric substance resol, silicon-dioxide and tensio-active agent
The mixing solutions that step 1 is made at room temperature continues to stir, and then mixing solutions is transferred in the reaction vessel of sealing and is carried out after hydrothermal treatment consists, removes supernatant liquid and is precipitated thing, obtains pressed powder after dry; Gained pressed powder is the complex body of polymkeric substance resol, silicon-dioxide and tensio-active agent;
The temperature of described hydrothermal treatment consists is 50～200 ℃;
Step 3: high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
The pressed powder that step 2 is obtained high-temperature calcination under protection of inert gas makes its carbonization, obtains black solid powder; Gained black solid powder is the complex body of carbon material and silicon-dioxide;
Step 4: the making of multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial
The black solid powder that step 3 is obtained soaks with aqueous hydrogen fluoride solution or strong base solution, removes silicon-dioxide, obtains multilevel hierarchy meso-porous carbon material;
The high-temperature calcination in air of the black solid powder of the pressed powder of step 2 gained or step 3 gained is obtained to multilevel hierarchy Metaporous silicon dioxide material.
2. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: the alcohols described in step 1 is the alcohols that carbonatoms is less than 5.
3. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: water and alcohols described in step 1 are hybridly prepared into reaction solvent, and wherein the volume ratio of alcohols and water is 4: 3～4: 52.
4. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: the catalyzer alkali described in step 1 for can ionizing the reagent that produces hydroxide ion in water.
5. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: after the catalyzer alkali described in step 1 adds, the mass concentration of alkali reagent in water and alcohols reaction solvent is 0.8～8g/L.
6. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: after the Resorcinol described in step 1 adds, its mass concentration in water and alcohols reaction solvent is not more than 3%; After cetyl trimethylammonium bromide described in step 1 adds, its mass concentration in water and alcohols reaction solvent is not more than 3%; The mass concentration of the formaldehyde solution described in step 1 is not less than 30%, and adding the mol ratio of Resorcinol and formaldehyde after formaldehyde solution is 1: 1.2～1: 2.5; The volume ratio of the add-on of the tetraethoxysilane described in step 1 and water and alcohols reaction solvent can be 0.25: 28～and 3: 28.
7. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: the rare gas element described in step 3 is any gas except oxygen or the mixed gas of oxygen-free gas.
8. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: the condition of the high-temperature calcination described in step 3, step 4 is that temperature is not less than 300 ℃.
9. a kind of method of simultaneously preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial as claimed in claim 1, is characterized in that: in the aqueous hydrogen fluoride solution described in step 4 or strong base solution, contained solute massfraction is 5wt%～20wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618735A (en) * | 2003-11-19 | 2005-05-25 | 中国科学院金属研究所 | Synthesis method of monodispersed nano-mesopore silicon dioxide material |
| CN1821182A (en) * | 2006-01-26 | 2006-08-23 | 复旦大学 | Method for preparing mesoporous carbon material |
| CN101041428A (en) * | 2007-03-08 | 2007-09-26 | 复旦大学 | Multi-stage ordered medium hole/big hole composite material and preparation method thereof |
| CN101610836A (en) * | 2006-05-25 | 2009-12-23 | 通用汽车环球科技运作公司 | Carbon and carbon composite with highly ordered mesosize pores |
| CN102259871A (en) * | 2011-05-20 | 2011-11-30 | 上海大学 | Method for synthesizing mesoporous silicon dioxide nanotube by layer-by-layer (LBL) method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100628031B1 (en) * | 2005-07-27 | 2006-09-26 | (주) 나노텍 | Thermally improve conductive carbon sheet base on mixed carbon material of expanded graphite powder and carbon nano tube powder |
-
2012
- 2012-05-10 CN CN201210145019.6A patent/CN102642843B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618735A (en) * | 2003-11-19 | 2005-05-25 | 中国科学院金属研究所 | Synthesis method of monodispersed nano-mesopore silicon dioxide material |
| CN1821182A (en) * | 2006-01-26 | 2006-08-23 | 复旦大学 | Method for preparing mesoporous carbon material |
| CN101610836A (en) * | 2006-05-25 | 2009-12-23 | 通用汽车环球科技运作公司 | Carbon and carbon composite with highly ordered mesosize pores |
| CN101041428A (en) * | 2007-03-08 | 2007-09-26 | 复旦大学 | Multi-stage ordered medium hole/big hole composite material and preparation method thereof |
| CN102259871A (en) * | 2011-05-20 | 2011-11-30 | 上海大学 | Method for synthesizing mesoporous silicon dioxide nanotube by layer-by-layer (LBL) method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108779342A (en) * | 2016-03-31 | 2018-11-09 | 陶氏环球技术有限责任公司 | The method for preparing hydrophobic silica particles |
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