CN103553018A - Regular microporous carbon preparation method - Google Patents
Regular microporous carbon preparation method Download PDFInfo
- Publication number
- CN103553018A CN103553018A CN201310359617.8A CN201310359617A CN103553018A CN 103553018 A CN103553018 A CN 103553018A CN 201310359617 A CN201310359617 A CN 201310359617A CN 103553018 A CN103553018 A CN 103553018A
- Authority
- CN
- China
- Prior art keywords
- regular
- microporous carbon
- regular microporous
- prepolymer solution
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to a regular microporous carbon preparation method, which comprises: weighing phloroglucinol, terephthalaldehyde and dioxane according to a mass ratio of 1:0.7-0.9:3.4-17.2, and carrying out a reaction for 15-120 min at a temperature of 70 DEG C under a stirring speed of 400-1000 rotation/min to obtain a phenol formaldehyde prepolymer solution; introducing nitrogen for 10-30 min to the prepolymer solution to expel oxygen, transferring to a reaction kettle, and carrying out a heat treatment for 2-5 d at a temperature of 200-240 DEG C to obtain a regular microporous polymer; and in a tubular furnace, under the protection of an inert gas, heating the regular microporous polymer to achieve a temperature of 800-1000 DEG C according to a heating rate of 0.5-10 DEG C/min to carry out carbonization, and naturally cooling to achieve a room temperature to obtain the regular microporous carbon. Acoording to the present invention, the particle size of the prepared regular microporous carbon can be adjusted within a range of 10 nm-4.0 mum, the pore is the micropore and is regular, and the regular microporous carbon has important application prospects in fields of energy source storage, absorption and separation, catalysis and the like.
Description
Technical field
The present invention relates to a kind of preparation method of regular microporous carbon.Belong to technical field of material.
Background technology
The advantages such as micro-pore carbon material has that specific surface area is high, physicochemical property are stable, are widely used in the fields such as energy storage, absorption and separated and heterogeneous catalyst.For example, " preparation method of biomass high specific surface micro-pore carbon material " (Chinese invention patent, the patent No.: ZL200710055490.5), " preparation method with the formed active carbon electrode of high specific capacitance " (Chinese invention patent, the patent No.: ZL02130063.1), " preparation method of high absorption property gac " (Chinese invention patent, the patent No.: ZL02157271.2), " deodorizing method of a kind of hydrogen sulphide removing material and charcoal absorption and treatment unit " (Chinese invention patent, the patent No.: ZL200710040050.2) and " activated-carbon catalyst with and its preparation method and application " (Chinese invention patent, application number: 201110225328.X) etc.Yet, there are a large amount of tortuous, irregular ducts of island in most of microporous carbon, it is very limited in actual applications, for example, common microporous carbon is when as electrode material for super capacitor, and irregular duct makes electrolyte ion be difficult to effectively enter, and specific surface area utilization ratio reduces, ion transport is obstructed, thereby causes its pulse high current charge-discharge performance to be very limited; In addition, common microporous carbon is when as gas adsorption material and catalyzer, and the diffusion of guest molecule and transmission meeting are hindered by irregular micro channel, thereby restriction guest molecule is to transmission and the diffusion in the active centre in micropore.Therefore, research worker transfers to emphasis by the pore passage structure optimization of traditional micro-pore carbon material, prepares regular micro-pore carbon material.For example, " porous charcoal with template charring preparation with regular texture and high-specific surface area " (Chinese invention patent, patent No.: ZL200510046708.1) reported that take zeolite has the microporous carbon of regular texture as template preparation.The micro channel of rule is conducive to guest molecule/electrolyte ion rapid diffusion and transmission.But, in this preparation process, first need to prepare zeolite as template, then need again strong acid or highly basic to remove zeolite template, this can increase preparation time and the cost of material undoubtedly, and the use meeting of preparation process strong acid or highly basic causes disadvantageous effect to environment.
Summary of the invention
The object of the invention is to disclose a kind of preparation method of regular microporous carbon.The diameter of the regular microporous carbon of preparing by method of the present invention is adjustable within the scope of the μ m of 10nm～4.0, has the regular micropore that is about 0.5nm, and its specific surface area can reach 500m
2more than/g, pore volume reaches 0.2cm
3more than/g.
In order to achieve the above object, Phloroglucinol and terephthalaldehyde that the present invention's selection has rigid structure are carbon source, by heat polymerization, obtain phenolic aldehyde performed polymer, and then regular microporous carbon is prepared in charing.The method can come the particle diameter of control law microporous carbon adjustable within the scope of the μ m of 10nm～4.0 by changing the concentration of phenolic aldehyde performed polymer easily and effectively.
Concrete technique is undertaken by following several steps:
First by Phloroglucinol: terephthalaldehyde: dioxane=1:0.7～0.9:3.4～17.2 mass ratio measures, under the stirring velocity of 400～1000 revs/min, in 70 ℃ of reaction 15～120min, obtain phenolic aldehyde prepolymer solution.In this phenolic aldehyde prepolymer solution, lead to nitrogen 10～30min expeling oxygen again, then transfer them in reactor, in 200～240 ℃ of thermal treatment 2～5d, obtain regular microporous polymer.Then in tube furnace, under protection of inert gas, by the temperature rise rate of 0.5～10 ℃/min, gained rule microporous polymer is heated to 800～1000 ℃ of charings, is finally naturally cooled to room temperature and obtains regular microporous carbon.
Above-mentioned rare gas element is selected a kind of in nitrogen, argon gas, helium;
Above-mentioned raw materials is commercially available technical grade product.
Tool of the present invention has the following advantages:
1. the present invention is by having Phloroglucinol and terephthalaldehyde polymerization formation rule microporous polymer in organic solvent of rigid structure, then by charing, prepare regular microporous carbon, in preparation process, do not need to use any template and catalyzer, do not need strong acid or highly basic yet, therefore, the method has the advantages such as technique is simple, environmental protection.
2. the invention solves and in conventional micro-pore carbon material, have the irregular shortcoming in duct.Phloroglucinol and terephthalaldehyde polymerization form organic framework material microporous polymer, and after charing, the microporous carbon of gained has the regular micropore that aperture is about 0.5nm.The specific surface area of the regular microporous carbon that in addition, prepared by the present invention can reach 500m
2more than/g, pore volume reaches 0.2cm
3more than/g.
3. the present invention can be by changing the reaction density of phenolic aldehyde performed polymer, and the particle diameter of control law microporous carbon is adjustable within the scope of the μ m of 10nm～4.0 effectively, and therefore, the present invention can prepare the regular microporous carbon particle that is applicable to practical application and concrete dimensional requirement.
Embodiment
Embodiment 1
By Phloroglucinol: terephthalaldehyde: dioxane=1:0.7:3.4 mass ratio measures, under the stirring velocity of 400 revs/min, in 70 ℃ of reaction 15min, obtains phenolic aldehyde prepolymer solution.In this phenolic aldehyde prepolymer solution, lead to the oxygen in nitrogen 10min expeling phenolic aldehyde prepolymer solution, then transfer them in reactor, in 200 ℃ of thermal treatment 2d, obtain regular microporous polymer.In tube furnace, under protection of inert gas, by the temperature rise rate of 0.5 ℃/min, gained rule microporous polymer is heated to 800 ℃ of charings, be finally naturally cooled to room temperature and obtain the regular microporous carbon that particle diameter is about 10nm.
Embodiment 2
By Phloroglucinol: terephthalaldehyde: dioxane=1:0.75:6.9 mass ratio measures, under the stirring velocity of 600 revs/min, in 70 ℃ of reaction 30min, obtains phenolic aldehyde prepolymer solution.In this phenolic aldehyde prepolymer solution, lead to oxygen in nitrogen 15min expeling phenolic aldehyde prepolymer solution, then transfer them in reactor, in 210 ℃ of thermal treatment 3d, obtain regular microporous polymer.In tube furnace, under protection of inert gas, by the temperature rise rate of 1 ℃/min, gained rule microporous polymer is heated to 850 ℃ of charings, be finally naturally cooled to room temperature and obtain the regular microporous carbon that particle diameter is about 30nm.
Embodiment 3
By Phloroglucinol: terephthalaldehyde: dioxane=1:0.8:10.3 mass ratio measures, under the stirring velocity of 800 revs/min, in 70 ℃ of reaction 60min, obtains phenolic aldehyde prepolymer solution.In this phenolic aldehyde prepolymer solution, lead to the oxygen in nitrogen 20min expeling phenolic aldehyde prepolymer solution, then transfer them in reactor, in 220 ℃ of thermal treatment 4d, obtain regular microporous polymer.In tube furnace, under protection of inert gas, by the temperature rise rate of 2 ℃/min, gained rule microporous polymer is heated to 900 ℃ of charings, be finally naturally cooled to room temperature and obtain the regular microporous carbon that particle diameter is about 30nm.
Embodiment 4
By Phloroglucinol: terephthalaldehyde: dioxane=1:0.85:13.8 mass ratio measures, under the stirring velocity of 900 revs/min, in 70 ℃ of reaction 90min, obtains phenolic aldehyde prepolymer solution.In this phenolic aldehyde prepolymer solution, lead to oxygen in nitrogen 25min expeling phenolic aldehyde prepolymer solution, then transfer them in reactor, in 230 ℃ of thermal treatment 4d, obtain regular microporous polymer.In tube furnace, under protection of inert gas, by the temperature rise rate of 5 ℃/min, gained rule microporous polymer is heated to 950 ℃ of charings, be finally naturally cooled to room temperature and obtain the regular microporous carbon that particle diameter is about 2.0 μ m.
Embodiment 5
By Phloroglucinol: terephthalaldehyde: dioxane=1:0.9:17.2 mass ratio measures, under the stirring velocity of 1000 revs/min, in 70 ℃ of reaction 120min, obtains phenolic aldehyde prepolymer solution.Adopt in this phenolic aldehyde prepolymer solution and lead to oxygen in nitrogen 30min expeling phenolic aldehyde prepolymer solution, then transfer them in reactor, in 240 ℃ of thermal treatment 5d, obtain regular microporous polymer.In tube furnace, under protection of inert gas, by the temperature rise rate of 10 ℃/min, gained rule microporous polymer is heated to 1000 ℃ of charings, be finally naturally cooled to room temperature and obtain the regular microporous carbon that particle diameter is about 4.0 μ m.
After measured, the aperture of the regular microporous carbon of embodiment 1-5 gained is about 0.5nm, and specific surface area reaches 500m
2more than/g, pore volume reaches 0.2cm
3more than/g.
Above raw material is commercially available technical grade product.
The micro channel of rule is conducive to guest molecule/electrolyte ion rapid diffusion and the transmission in the fields such as energy storage, absorption and separated and catalysis.The regular microporous carbon of embodiment 1-5 gained can be used for making the electrode materials of ultracapacitor.Take in mass ratio the regular microporous carbon obtaining in embodiment 1-5: the ptfe emulsion of 12wt% (buying from Shanghai Sanaifu New Material Co., Ltd): graphite=8:1:1, after mixing, under infrared lamp, dry, by drying sample, under the pressure of 10MPa, be pressed on nickel foam (buying from Liyuan New Material Co Ltd, Changsha), in 80 ℃ of vacuum-drying 24h, make electrode of super capacitor.Take this electrode as working electrode, and foam nickel electrode is to electrode, and Ag/AgCl electrode is reference electrode, and 6mol/L KOH solution is electrolytic solution, the chemical property of test job electrode.When current density is 10A/g, regular microporous carbon can reach 156F/g as the ratio electric capacity of electrode of super capacitor; When current density is increased to 50A/g, more than it still can remain on 100F/g than electric capacity.
Claims (1)
1. the preparation method of a regular microporous carbon, it is characterized in that: first by Phloroglucinol: terephthalaldehyde: dioxane=1:0.7～0.9:3.4～17.2 mass ratio measures, under the stirring velocity of 400～1000 revs/min, in 70 ℃ of reaction 15～120min, obtain phenolic aldehyde prepolymer solution; In this prepolymer solution, lead to nitrogen 10～30min expeling oxygen again, then transfer them in reactor, in 200～240 ℃ of thermal treatment 2～5d, obtain regular microporous polymer; Then, in tube furnace, under protection of inert gas, by the temperature rise rate of 0.5～10 ℃/min, gained rule microporous polymer is heated to 800～1000 ℃ of charings, is finally naturally cooled to room temperature and obtains regular microporous carbon;
Above-mentioned rare gas element is selected a kind of in nitrogen, argon gas, helium;
Above-mentioned raw materials is commercially available technical grade product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310359617.8A CN103553018A (en) | 2013-08-16 | 2013-08-16 | Regular microporous carbon preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310359617.8A CN103553018A (en) | 2013-08-16 | 2013-08-16 | Regular microporous carbon preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103553018A true CN103553018A (en) | 2014-02-05 |
Family
ID=50007443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310359617.8A Pending CN103553018A (en) | 2013-08-16 | 2013-08-16 | Regular microporous carbon preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103553018A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663569A (en) * | 2019-02-14 | 2019-04-23 | 齐鲁工业大学 | A kind of micro-pore carbon material and preparation method thereof |
| CN111326349A (en) * | 2020-03-03 | 2020-06-23 | 华东师范大学 | PIM-1 loaded polypyrrole composite material, and preparation method and application thereof |
| CN114684808A (en) * | 2022-05-10 | 2022-07-01 | 大连理工大学 | Preparation method of porous nano carbon material and application of porous nano carbon material in separation of propylene/propane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010135389A2 (en) * | 2009-05-20 | 2010-11-25 | Ut-Battelle, Llc | Mesoporous carbon materials |
| CN102963876A (en) * | 2012-10-31 | 2013-03-13 | 同济大学 | Preparation method of microporous carbon material |
| CN102976304A (en) * | 2012-11-16 | 2013-03-20 | 同济大学 | Preparation method of porous carbon nanosphere with controllable diameter |
-
2013
- 2013-08-16 CN CN201310359617.8A patent/CN103553018A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010135389A2 (en) * | 2009-05-20 | 2010-11-25 | Ut-Battelle, Llc | Mesoporous carbon materials |
| CN102963876A (en) * | 2012-10-31 | 2013-03-13 | 同济大学 | Preparation method of microporous carbon material |
| CN102976304A (en) * | 2012-11-16 | 2013-03-20 | 同济大学 | Preparation method of porous carbon nanosphere with controllable diameter |
Non-Patent Citations (1)
| Title |
|---|
| ALEXANDROS P. KATSOULIDIS， ET AL.: "Phloroglucinol Based Microporous Polymeric Organic Frameworks with -OH Functional Groups and High CO2 Capture Capacity", 《CHEMISTRY OF MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663569A (en) * | 2019-02-14 | 2019-04-23 | 齐鲁工业大学 | A kind of micro-pore carbon material and preparation method thereof |
| CN109663569B (en) * | 2019-02-14 | 2021-03-02 | 齐鲁工业大学 | Microporous carbon material and preparation method thereof |
| CN111326349A (en) * | 2020-03-03 | 2020-06-23 | 华东师范大学 | PIM-1 loaded polypyrrole composite material, and preparation method and application thereof |
| CN114684808A (en) * | 2022-05-10 | 2022-07-01 | 大连理工大学 | Preparation method of porous nano carbon material and application of porous nano carbon material in separation of propylene/propane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102774824B (en) | Method for preparing graphene crosslinked type organic aerogel and carbon aerogel by normal-pressure drying | |
| Liang et al. | Popcorn-derived porous carbon for energy storage and CO2 capture | |
| Zhu et al. | Activated carbon produced from paulownia sawdust for high-performance CO2 sorbents | |
| CN105780198B (en) | A kind of preparation method of order mesoporous carbon nano-fiber | |
| CN102718205B (en) | Method for preparing three-dimensional hierarchical porous carbon | |
| Shi et al. | Nitrogen doped hierarchically porous carbon derived from glucosamine hydrochloride for CO2 adsorption | |
| CN106120027B (en) | A kind of preparation method of high porosity mesoporous nano-graphene fiber | |
| CN106757539B (en) | A kind of preparation method of Fe-Mn cycle and transference porous carbon | |
| Shen et al. | Hollow porous carbon fiber from cotton with nitrogen doping | |
| CN104715936B (en) | A kind of classifying porous carbon electrode material and preparation method for ultracapacitor | |
| CN102963876A (en) | Preparation method of microporous carbon material | |
| CN107628597B (en) | By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method | |
| Li et al. | Fabrication of carbon microspheres with controllable porous structure by using waste Camellia oleifera shells | |
| CN110589827A (en) | Method for preparing biomass carbon aerogel by double activation method and application thereof | |
| CN111151285B (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| Wang et al. | Superwetting monolithic carbon with hierarchical structure as supercapacitor materials | |
| CN104874381A (en) | Preparation method of carbon/carbon nano tube composite foam adsorption material | |
| CN105951218A (en) | Preparation of nano-carbon fiber with high specific surface area | |
| CN103833006A (en) | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor | |
| Chang et al. | Cost-efficient strategy for sustainable cross-linked microporous carbon bead with satisfactory CO2 capture capacity | |
| CN104326470A (en) | Method for preparing high specific surface area micron-scale spherical activated carbon from carboxymethyl cellulose | |
| CN103553018A (en) | Regular microporous carbon preparation method | |
| CN103721645A (en) | Carbon aerogel for electric adsorption electrode and preparation method for carbon aerogel | |
| CN103107024B (en) | A kind of nitrogenous mesoporous carbon/MnO 2composite material and preparation method thereof | |
| CN106517183A (en) | A low-cost simple preparing method for nitrogen-doped porous charcoal with a high specific surface area |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140205 |