CN103359705B - Grading-hole Carbon Materials and preparation method thereof - Google Patents
Grading-hole Carbon Materials and preparation method thereof Download PDFInfo
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- CN103359705B CN103359705B CN201310283959.6A CN201310283959A CN103359705B CN 103359705 B CN103359705 B CN 103359705B CN 201310283959 A CN201310283959 A CN 201310283959A CN 103359705 B CN103359705 B CN 103359705B
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Abstract
The invention discloses a kind of preparation method of grading-hole Carbon Materials.The present invention is elementary template with wood (bamboo) material, and tensio-active agent is secondary template, and lacquer resins is presoma, prepares the Carbon Materials with hierarchical porous structure by means of confinement self-assembly and high temperature carbonization process.Preparation process of the present invention is simple, save time fast, production cost be low, can biomass such as efficiency utilization wood (bamboo) material improve its added value, grading-hole Carbon Materials prepared by the present invention has the micropore of high specific surface area and classification, mesoporous and macropore ternary nano structure, is with a wide range of applications in fields such as catalysis, absorption, separation, energy storage.
Description
Technical field
The present invention relates to Material Field, be specially a kind of grading-hole Carbon Materials and preparation method thereof.
Background technology
Grading-hole Carbon Materials has aperture controllable, and the ternary pore structure of micropore, mesoporous and macropore reasonable layout.In catalytic applications, its macropore can provide efficient mass transfer space, greatly can reduce diffusional resistance; Mesoporous transmission path drastically increases the rate of diffusion of ion, is conducive to the transmission of reactant and product; And micropore can improve the degree of scatter of reactive material, and provide abundant active centre, positive promoter action is served to catalytic effect.Thus, grading-hole Carbon Materials all has a wide range of applications in fields such as catalysis, absorption, separation, energy storage.At present, the preparation method of grading-hole Carbon Materials mainly contains template, template-activation coupling method, exempts from template, and their raw materials and template mostly are Chemicals.Along with the shortage of the energy and the continuous deterioration of environment, how directly to utilize natural biomass as raw material, and by simple, effectively and the method for low cost prepare the grading-hole material with particular topology structure and day by day become most important.
Wood (bamboo) material has the test-tube baby structure (pore structure) of unidirectional array, the test-tube baby tissue of its fibrous tissue from the cell envelope structure of nanometer scale to micron dimension, arrive the annual ring of millimeter magnitude again, define the biological structure features such as unique multi-level, test-tube baby structure, threadiness and anisotropy.The principal constituent of wood (bamboo) material is xylogen, Mierocrystalline cellulose and hemicellulose, and in main component, carbon accounts for 44%.Thus, wood (bamboo) material not only can make the stay in place form of biomimesis synthesis, and can as carbon source and the stay in place form preparing carbide composite material.In addition, compared with the material coming from industrial chemicals with other, the outstanding advantage of wood (bamboo) material is its " renewable " property and " environmental protection " to meet the strategic idea of human social.Undoubtedly, there is in the matrix material that the natural anisotropy graded porous structure of wood (bamboo) material has a special microstructure grading-hole in preparation the advantageous advantage that other stay in place form can not be compared.
Compare " soft template method " in traditional sense, solvent evaporates induction self-assembly method has: the selection diversity more of (1) solvent, precursor; (2) precursor and template do not need phase-splitting from solution to be precipitated out, and reduce the control overflow of precursor and template molecule being worked in coordination with to assembling; (3) preparation process simple to operate, save time fast.Therefore, solvent evaporates induction self-assembly method can be widely used in the preparation process of multiple mesoporous material.Obviously, reasonably utilize wood (bamboo) material biological template in conjunction with solvent evaporates induction self assembling process, by preparation has unique micropore, hierarchical porous structure functional materials that is mesoporous and macropore provides new approaches for us.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of grading-hole Carbon Materials.The present invention is elementary template with wood (bamboo) material, and tensio-active agent is secondary template, and lacquer resins is presoma, prepares the Carbon Materials with hierarchical porous structure by means of confinement self-assembly and high temperature carbonization process.Preparation process of the present invention is simple, save time fast, production cost be low, can the biological material such as efficiency utilization wood (bamboo) material improve its added value, grading-hole Carbon Materials prepared by the present invention has high specific surface area and graduate micropore, mesoporous and macroporous structure.
Technical problem solved by the invention realizes by the following technical solutions:
A preparation method for grading-hole Carbon Materials, comprises the steps:
At (1) 25 ~ 40 DEG C, a certain amount of tensio-active agent being dissolved in mass ratio is 1:(20 ~ 100) ethanol in, then add low order resol, fully stir and obtain clear soln.
(2) pretreated wood (bamboo) powder is joined airtight vacuum pressurized tank, vacuumize, then inject a certain amount of step (1) solution, negative pressure of vacuum dipping 30 ~ 60 minutes.Take out, at 30 ~ 60 DEG C, volatilization is except desolventizing, drying, then solidifies 6 ~ 36 hours at 100 ~ 150 DEG C.
(3) under protective atmosphere, step (2) gained crude product is placed in charring furnace 600 ~ 1200 DEG C charing 3 ~ 6 hours, temperature rise rate is 3 ~ 8 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Described tensio-active agent is the one in the triblock copolymer such as polyethylene oxide-poly(propylene oxide), oxyethane-polybutylene oxide, as being preferably non-ionic surfactant F127.
Described low order resol (M
w<500) known technology can be passed through: as the base catalyzed reactions preparation between phenolic aldehyde and formaldehyde.
Be 30 ~ 300 orders sized by described wood (bamboo) powder, the mass ratio of wood powder and precursor liquid is 1:(1 ~ 9).
Described reducing atmosphere is a kind of in nitrogen, argon gas or both mixing, as being preferably argon gas.
Described high temperature carbonization is 600 ~ 1200 DEG C.
beneficial effect:
The present invention is compared with existing " template ", " template-activation coupling method ", " exempting from template " etc., tool has the following advantages: (1) is first template with wood (bamboo) material, tensio-active agent secondary template, lacquer resins is presoma, utilizes confinement self-assembly and high temperature carbonization process to prepare to have the Carbon Materials of the hierarchical porous structure of micropore, mesoporous and macropore; (2) preparation process is simple, saves time fast, production cost is low; (3) effectively can utilize the biomass innovative development grading-hole Carbon Materials such as low-quality wood (bamboo) material, wood (bamboo) material residuum, improve its added value.
Accompanying drawing explanation
Fig. 1 is the little angle x-ray diffraction pattern of grading-hole Carbon Materials prepared by embodiment 5.
Fig. 2 is the scanning electron microscope (SEM) photograph of grading-hole Carbon Materials prepared by embodiment 5.
Fig. 3 is the transmission electron microscope picture (a) of grading-hole Carbon Materials prepared by embodiment 5.
Fig. 4 is the transmission electron microscope picture (b) of grading-hole Carbon Materials prepared by embodiment 5.
Fig. 5 is the N of grading-hole Carbon Materials prepared by embodiment 5
2adsorption-desorption curve (a).
Fig. 6 is the pore size distribution curve (b) of grading-hole Carbon Materials prepared by embodiment 5.
Embodiment
Give an actual example below and describe the present invention.
Embodiment 1:
(1) by the melting at 40 ~ 42 DEG C of 6.1g phenol, add 1.3g mass percent be 20% the NaOH aqueous solution stir 10 minutes, quick instillation 10.5g concentration is the formalin of 37%, be warming up to 70 ~ 75 DEG C of reactions 1 hour, be cooled to room temperature, by the pH value of the HCI solution regulator solution of 0.6M close to 7.0, in 50 ~ 52 DEG C of vacuum decompressions dehydrations 1 ~ 2 hour.The thick liquid obtained is dissolved in 80g ethanol, and being made into mass percent is that 40% homogeneous solution is stand-by.
At (2) 25 DEG C, get 6.15gF127 and be dissolved in 43.1g ethanol, stir 2 hours, then add the low order phenol resin solution that 30g step (1) prepares, continue stirring 1 hour, obtain settled solution.
(3) wood (bamboo) powder after 10g alligatoring is transferred to airtight vacuum pressed tank, be evacuated to 0.09Mpa, then inject the solution that 80g step (2) prepares, negative pressure of vacuum floods 45 minutes, slow emptying.Take out wood (bamboo) powder after dipping, at being placed in unlimited vessel 35 DEG C, volatilization is except desolventizing, drying, then solidifies 8 hours at 105 DEG C.
(4) under argon atmosphere, step (3) gained crude product is placed in charring furnace 700 DEG C charing 4 hours, temperature rise rate is 3 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Embodiment 2:
(1) by the melting at 40 ~ 42 DEG C of 6.1g phenol, add at such a temperature 1.3g mass percent be 20% the NaOH aqueous solution stir 10 minutes, add the formalin that 10.5g concentration is 37%, be warming up to 70 ~ 75 DEG C of reactions 1 hour, be cooled to room temperature, by the pH value of 0.6MHCI solution regulator solution close to 7.0, in 50 ~ 52 DEG C of vacuum decompressions dehydrations 1 ~ 2 hour.The thick liquid obtained being dissolved in 80g ethanol, to be made into mass percent be that 40% homogeneous solution is stand-by.
At (2) 40 DEG C, get 10gF127 and be dissolved in 70g ethanol, stir 2 hours, then add the low order resol ethanolic soln that 50g step (1) prepares, continue stirring 1 hour, obtain clear sol.
(3) wood (bamboo) powder after 10g alligatoring is transferred to airtight vacuum pressurized tank, be evacuated to 0.09Mpa, then inject the solution that 130g step (2) prepares, negative pressure of vacuum floods 60 minutes, slow emptying.Take out wood (bamboo) powder after dipping, be placed in unlimited vessel and volatilize except desolventizing, drying at 40 DEG C, then solidify 6 hours at 150 DEG C.
(4) under nitrogen protection atmosphere, step (3) gained crude product is placed in charring furnace 900 DEG C charing 4.5 hours, temperature rise rate is 4 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Embodiment 3:
(1) by the melting at 40 ~ 42 DEG C of 6.1g phenol, add at such a temperature 1.3g mass percent be 20% the NaOH aqueous solution stir 10 minutes, add the formalin that 10.5g concentration is 37%, be warming up to 70 ~ 75 DEG C of reactions 1 hour, be cooled to room temperature, by the pH value of 0.6MHCI solution regulator solution close to 7.0, in 50 ~ 52 DEG C of vacuum decompressions dehydrations 1 ~ 2 hour.The thick liquid obtained being dissolved in 80g ethanol, to be made into mass percent be that 40% homogeneous solution is stand-by.
At (2) 30 DEG C, get 4.62gF127 and be dissolved in 32.3g ethanol, stir 1.5 hours, then add the low order resol ethanolic soln that 23.08g step (1) prepares, continue stirring 1.5 hours, obtain clear sol.
(3) wood (bamboo) powder after 10 alligatoring is transferred to airtight vacuum pressurized tank, be evacuated to 0.09Mpa, then inject the solution that 60g step (2) prepares, negative pressure of vacuum floods 30 minutes, slow emptying.Take out wood (bamboo) powder after dipping, at being placed in unlimited vessel 45 DEG C, volatilization is except desolventizing, drying, then solidifies 10 hours at 100 DEG C.
(4) under argon atmosphere, step (3) gained crude product is placed in charring furnace 700 DEG C charing 3 hours, temperature rise rate is 6 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Embodiment 4:
(1) by the melting at 40 ~ 42 DEG C of 6.1g phenol, add at such a temperature 1.3g mass percent be 20% the NaOH aqueous solution stir 10 minutes, add the formalin that 10.5g concentration is 37%, be warming up to 70 ~ 75 DEG C of reactions 1 hour, be cooled to room temperature, by the pH value of 0.6MHCI solution regulator solution close to 7.0, in 50 ~ 52 DEG C of vacuum decompressions dehydrations 1 ~ 2 hour.The thick liquid obtained being dissolved in 80g ethanol, to be made into mass percent be that 40% homogeneous solution is stand-by.
At (2) 30 DEG C, get 7.69gF127 and be dissolved in 53.85g ethanol, stir 1 hour, then add the low order resol ethanolic soln that 38.46g step (1) prepares, continue stirring 1.5 hours, obtain settled solution.
(3) wood (bamboo) powder after 10 alligatoring is transferred to airtight vacuum pressurized tank, be evacuated to 0.09Mpa, then inject the solution that 100g step (2) prepares, negative pressure of vacuum floods 30 minutes, slow emptying.Take out wood (bamboo) powder after dipping, be placed in unlimited vessel and volatilize except desolventizing, drying at 45 DEG C, then solidify 12 hours at 105 DEG C.
(4) under nitrogen protection atmosphere, step (3) gained crude product is placed in charring furnace 700 DEG C charing 3 hours, temperature rise rate is 5 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Embodiment 5:
(1) by the melting at 40 ~ 42 DEG C of 6.1g phenol, add at such a temperature 1.3g mass percent be 20% the NaOH aqueous solution stir 10 minutes, add the formalin that 10.5g concentration is 37%, be warming up to 70 ~ 75 DEG C of reactions 1 hour, be cooled to room temperature, by the pH value of 0.6MHCI solution regulator solution close to 7.0, in 50 ~ 52 DEG C of vacuum decompressions dehydrations 1 ~ 2 hour.The thick liquid obtained being dissolved in 80g ethanol, to be made into mass percent be that 40% homogeneous solution is stand-by.
At (2) 40 DEG C, get 12gF127 and be dissolved in 84g ethanol, stir 1 hour, then add the solution that 60g step (1) is prepared, continue stirring 1 hour, obtain settled solution.
(3) wood (bamboo) powder after 10g alligatoring is transferred to airtight vacuum pressurized tank, be evacuated to 0.095Mpa, then inject the solution that 130g step (2) prepares, negative pressure of vacuum floods 60 minutes, slow emptying.Take out wood (bamboo) powder after dipping, at being placed in unlimited vessel 40 DEG C, volatilization is except desolventizing, drying, then solidifies 24 hours at 120 DEG C.
(4) under argon atmosphere, step (3) gained crude product is placed in charring furnace 900 DEG C charing 4 hours, temperature rise rate is 3 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
Fig. 1 executes the little angle x-ray diffraction pattern of the grading-hole Carbon Materials prepared by example for this, can find out, this matrix material has obvious mesoscopic structure characteristic diffraction peak.
The scanning electron microscope (SEM) photograph of the grading-hole Carbon Materials of Fig. 2 prepared by this embodiment, can find out the microtexture of this material, maintains the natural micropore structure of first template (timber).
The transmission electron microscope picture of the grading-hole Carbon Materials of Fig. 3,4 prepared by this embodiment, as shown in figure (a) and (b), illustrates micropore and the meso-hole structure of this matrix material clearly.
The N of the grading-hole Carbon Materials of Fig. 5 and Fig. 6 prepared by this embodiment
2adsorption-desorption curve (a) and corresponding pore size distribution curve (b).Adopt the specific surface area of the ASAP2010 nitrogen adsorption instrument test grading hole Carbon Materials of Micromeritics company of the U.S., pore volume and pore size distribution.Result shows, the specific surface area of this material is 568.3m
2/ g, pore volume is 0.35cm
3/ g.From nitrogen adsorption isothermal curve, can find out to there is obvious micropore and mesoporous adsorpting characteristic, consistent with TEM test result.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. a preparation method for grading-hole Carbon Materials, is characterized in that, comprises the steps:
At (1) 25 ~ 40 DEG C, getting proper amount of surfactant is dissolved in a certain amount of ethanol, then low order resol is added, abundant stirring obtains clear soln, described tensio-active agent is triblock copolymer, and described triblock copolymer is the one in polyethylene oxide-poly(propylene oxide), oxyethane-polybutylene oxide;
(2) pretreated wood powder is joined airtight vacuum pressurized tank, vacuumize, then a certain amount of step (1) solution is injected, negative pressure of vacuum dipping 30 ~ 60 minutes, take out, at 30 ~ 60 DEG C, volatilization is except desolventizing, drying, then solidifies 6 ~ 36 hours at 100 ~ 150 DEG C;
(3) under protective atmosphere, step (2) gained crude product is placed in charring furnace high temperature carbonization 3 ~ 6 hours, temperature rise rate is 3 ~ 8 DEG C/min, can obtain a kind of grading-hole Carbon Materials.
2. the preparation method of a kind of grading-hole Carbon Materials according to claim 1, is characterized in that, described tensio-active agent and the mass ratio of ethanol are 1:(20 ~ 100); The mass ratio of low order resol and ethanol is 1:(6 ~ 40).
3. the preparation method of a kind of grading-hole Carbon Materials according to claim 1 and 2, is characterized in that, described tensio-active agent is F127.
4. the preparation method of a kind of grading-hole Carbon Materials according to claim 1 and 2, is characterized in that, described resol is low-molecular-weight lacquer resins prepolymer, Mw<500.
5. the preparation method of a kind of grading-hole Carbon Materials according to claim 1 and 2, is characterized in that, described wood powder is 30 ~ 300 orders, and the mass ratio of the mixed solution of wood powder and step (1) is 1:(1 ~ 9).
6. the preparation method of a kind of grading-hole Carbon Materials according to claim 1, is characterized in that, described protective atmosphere is one in nitrogen, argon gas or both mixing.
7. the preparation method of a kind of grading-hole Carbon Materials according to claim 1, is characterized in that, the carbonization temperature described in step (3) is 600 ~ 1200 DEG C.
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| CN106564873B (en) * | 2016-11-08 | 2018-11-16 | 广西大学 | A kind of big micro-diplopore film carbon material and preparation method thereof |
| CN106475051B (en) * | 2016-11-08 | 2019-02-26 | 重庆文理学院 | A kind of high-performance adsorbent material and preparation method thereof |
| CN106517137B (en) * | 2016-11-09 | 2018-12-07 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of super hydrophilic biomimetic material |
| CN107381535B (en) * | 2017-09-15 | 2019-10-25 | 青岛科技大学 | A method of preparing ordered mesoporous carbon microballoon |
| CN109053216B (en) * | 2018-10-09 | 2021-09-24 | 中国科学院宁波材料技术与工程研究所 | Block material with wetting anisotropy and preparation method thereof |
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