CN102642843A - 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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- CN102642843A CN102642843A CN2012101450196A CN201210145019A CN102642843A CN 102642843 A CN102642843 A CN 102642843A CN 2012101450196 A CN2012101450196 A CN 2012101450196A CN 201210145019 A CN201210145019 A CN 201210145019A CN 102642843 A CN102642843 A CN 102642843A
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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 for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously.Belong to the meso-porous nano field of material preparation.
Background technology
Since 20th century, found the meliority of natural porous material the forties, people just began 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 the aperture is mesoporous between the hole of 2～50nm.MOBIL company used alkyl quaternary ammonium salts type cats product successfully to synthesize M41S mesoporous material (MCM-41, MCM-48, MCM-50) as template first in 1992; Thereby porous material is expanded to mesoporous from micropore, and between poromerics (like zeolite) and large pore material (like activated carbon), erected seat bridge fine strain of millet.
Mesoporous material; Like silicon-dioxide and carbon material; Because its big specific surface area and pore volume; Good thermostability and certain hydrothermal stability, and modifiable surface properties, regulatable macroscopical form and do not have plurality of advantages such as physiology toxicity, research fields such as heterogeneous catalyst, absorption and chromatographic separation, chemical sensor, biomedicine and high inorganic materials all show traditional inorganic porous material incomparable meliority and wide application prospect.
In recent years, because a lot of excellent properties of having of 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 ball; 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 each item advantage of mesoporous material simultaneously, and are widely used in medicament transport, bio-imaging, water treatment, support of the catalyst, a lot of aspects such as hard template and electrode materials.
The multilevel hierarchy Metaporous silicon dioxide material generally prepares with 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, present preparation method also rests on the method for hard template basically, and other comprise the also rare report of simple preparation method of soft template.In addition, traditional preparation method generally all is once can only prepare a kind of material, and this material has single specific pattern, for example hollow ball shape or piped mesoporous material.Therefore, invent a kind of simply, effectively can prepare the method for multilevel hierarchy mesoporous silicon oxide or carbon nanomaterial in large quantities, the application for this type material has very important significance.
Summary of the invention
The objective of the invention is in order to solve in the 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 for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously.
The objective of the invention is to realize through following technical scheme.
A kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously 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 can generate polymkeric substance resol after the reaction of Resorcinol and formaldehyde solution, tetraethoxysilane (TEOS) is hydrolyzed into silicon-dioxide;
Step 2: the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
The mixing solutions that step 1 is made at room temperature continues to stir, then with mixing solutions transfer to carry out hydrothermal treatment consists in the reaction vessel of sealing after, remove supernatant liquid and obtain throw out, obtain pressed powder after the drying; The 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
Pressed powder high-temperature calcination under protection of inert gas that step 2 is obtained makes its carbonization, obtains the 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 the multilevel hierarchy meso-porous carbon material.
The pressed powder of step 2 gained or black solid powder high-temperature calcination in air of step 3 gained are promptly obtained the multilevel hierarchy Metaporous silicon dioxide material.
The described alcohols of step 1 is all carbonatomss less than 5 alcohols, like methyl alcohol, and ethanol, n-propyl alcohol, Virahol, propyl carbinol, primary isoamyl alcohol etc. are preferably ethanol.
Described water of step 1 and alcohols are hybridly prepared into reaction solvent, and wherein the volume ratio of alcohols and water is 4: 3～4: 52.
The described catalyzer alkali of step 1 is all reagent that can ionization in water produce hydroxide ion, like sodium hydroxide, and ammonia soln etc.
After the described catalyzer alkali of step 1 added, the mass concentration of alkali reagent in water and alcohols reaction solvent was 0.8～8g/L.
After the described Resorcinol of step 1 added, its mass concentration in water and alcohols reaction solvent was not more than 3%.
After the described CTAB of step 1 added, its mass concentration in water and alcohols reaction solvent was not more than 3%.
The mass concentration of the described formaldehyde solution of step 1 is not less than 30%, and the mol ratio of Resorcinol and formaldehyde is 1: 1.2～1: 2.5 after the adding formaldehyde solution.
The volume ratio of the add-on of the described TEOS of 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 described hydrothermal treatment consists of step 2 is 50～200 ℃, is preferably 60～120 ℃.
The described rare gas element of step 3 can be any gas or the mixed gas of oxygen-free gas except oxygen.Be preferably nitrogen, argon gas.
The condition of step 3, the described high-temperature calcination of step 4 is that temperature is not less than 300 ℃.Temperature is preferably 400～1500 ℃,
Contained solute massfraction is preferably 5wt%～20wt% in described aqueous hydrogen fluoride solution of step 4 or the strong base solution.
Beneficial effect
1, a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously of the present invention, simple to operate, cost is lower, can realize scale operation.
2, the invention provides a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously, can obtain the mesoporous silicon oxide and the carbon nanomaterial of different-shape and structure through the proportioning of regulating water and alcohols reaction solvent.
3, the prepared material of the present invention can be used to environment, biology, catalysis, transmitter, various fields such as optics and electricity.
Description of drawings
Fig. 1 is preparing method's of the present invention schematic flow sheet;
Fig. 2 is the tubular, hollow mesoporous silicon oxide prepared among the embodiment 1 and ESEM (SEM) figure and transmission electron microscope (TEM) figure of carbon nanomaterial;
Fig. 3 is the hollow mesoporous silicon dioxide micro-sphere prepared among the embodiment 2 and the SEM figure and the TEM figure of eggshell-yolk structure (Rattle-type) mesoporous carbon Nano microsphere;
Fig. 4 is the radiation mesoporous silicon dioxide micro-sphere prepared among the embodiment 3 and the SEM figure and the TEM figure of hollow mesoporous carbon Nano microsphere.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
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; Adding 0.2mL mass concentration is 25%～30% ammonia soln, 0.2g Resorcinol and 0.2gCTAB in reaction solvent.
2, above-mentioned mixed solution is at room temperature stirred 30min, add 0.28mL formaldehyde solution and 1mL TEOS.
Two, the complex body of preparation 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 hydrothermal treatment consists 24h under 100 C temperature, removes supernatant liquid then and obtains throw out, obtains pressed powder after the drying; The 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
Pressed powder 600 C high-temperature calcination 4h under nitrogen protection that step 2 is obtained make its carbonization, obtain the 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 pressed powder of step 2 gained or black solid powder 600 C high-temperature calcination 6h in air of step 3 gained are promptly obtained the tubular, hollow mesopore silicon dioxide nano material.In the accompanying drawing 2, (a) be its SEM figure, (b c) is its TEM figure.
2, the black solid powder use mass concentration that step 3 is obtained is 10% aqueous hydrogen fluoride solution or strong base solution immersion, removes silicon-dioxide, obtains tubular, hollow mesoporous carbon nano material.Among Fig. 2, (d) be its SEM figure, (e f) is its TEM figure.
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 are hybridly prepared into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the 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 the 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 are hybridly prepared into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the radiation mesoporous silicon dioxide micro-sphere.In the 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 the 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 are mixedly configured into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 are mixedly configured into reaction solvent.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 in reaction solvent, to add the 1mL mass concentration.
2, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
Two, the preparation of superpolymer/silicon-dioxide/tensio-active agent complex body
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 in reaction solvent, to add the 0.1mL mass concentration.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 in reaction solvent, to add the 0.5mL mass concentration.
2, with 2 of the step 1 of embodiment 1.
Two, the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 in reaction solvent, to add the 0.2mL mass concentration.
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the 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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the 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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the 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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the 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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 the black solid powder use mass concentration that step 3 is obtained is 5% aqueous hydrogen fluoride solution or strong base solution immersion.
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 preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
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 it is that 20% aqueous hydrogen fluoride solution or strong base solution soak that black solid powder that step 3 obtains uses mass concentration.
Above-described specific descriptions; Purpose, technical scheme and beneficial effect to invention have carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; And be not used in qualification protection scope of the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously 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 can generate polymkeric substance resol after the reaction of Resorcinol and formaldehyde solution, tetraethoxysilane is hydrolyzed into silicon-dioxide;
Step 2: the complex body of preparation polymkeric substance resol, silicon-dioxide and tensio-active agent
The mixing solutions that step 1 is made at room temperature continues to stir, then with mixing solutions transfer to carry out hydrothermal treatment consists in the reaction vessel of sealing after, remove supernatant liquid and obtain throw out, obtain pressed powder after the drying; The gained pressed powder is the complex body of polymkeric substance resol, silicon-dioxide and tensio-active agent;
Step 3: high temperature cabonization obtains the complex body of carbon material and silicon-dioxide
Pressed powder high-temperature calcination under protection of inert gas that step 2 is obtained makes its carbonization, obtains the 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 the multilevel hierarchy meso-porous carbon material;
The pressed powder of step 2 gained or black solid powder high-temperature calcination in air of step 3 gained are promptly obtained the multilevel hierarchy Metaporous silicon dioxide material.
2. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: the described alcohols of step 1 for all carbonatomss less than 5 alcohols.
3. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: described water of step 1 and alcohols 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 for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: the described catalyzer alkali of step 1 is for can be in water can ionization producing the reagent of hydroxide ion.
5. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: after the described catalyzer alkali of step 1 added, the mass concentration of alkali reagent in water and alcohols reaction solvent was 0.8～8g/L.
6. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: after the described Resorcinol of step 1 added, its mass concentration in water and alcohols reaction solvent was not more than 3%; After the described CTAB of step 1 added, its mass concentration in water and alcohols reaction solvent was not more than 3%; The mass concentration of the described formaldehyde solution of step 1 is not less than 30%, and the mol ratio of Resorcinol and formaldehyde is 1: 1.2～1: 2.5 after the adding formaldehyde solution; The volume ratio of the add-on of the described TEOS of step 1 and water and alcohols reaction solvent can be 0.25: 28～and 3: 28.
7. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: the temperature of the described hydrothermal treatment consists of step 2 is 50～200 ℃.
8. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: the described rare gas element of step 3 is any gas or the mixed gas of oxygen-free gas except oxygen.
9. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: the condition of step 3, the described high-temperature calcination of step 4 is that temperature is not less than 300 ℃.
10. a kind of method for preparing multilevel hierarchy mesoporous silicon oxide and carbon nanomaterial simultaneously as claimed in claim 1 is characterized in that: contained solute massfraction is preferably 5wt%～20wt% in described aqueous hydrogen fluoride solution of step 4 or the strong base solution.
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