CN100540467C - A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof - Google Patents

A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof Download PDF

Info

Publication number
CN100540467C
CN100540467C CNB2006101483758A CN200610148375A CN100540467C CN 100540467 C CN100540467 C CN 100540467C CN B2006101483758 A CNB2006101483758 A CN B2006101483758A CN 200610148375 A CN200610148375 A CN 200610148375A CN 100540467 C CN100540467 C CN 100540467C
Authority
CN
China
Prior art keywords
preparation
fluorine functional
tensio
active agent
carbon material
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.)
Expired - Fee Related
Application number
CNB2006101483758A
Other languages
Chinese (zh)
Other versions
CN100999318A (en
Inventor
万颖
钱旭芳
张蝶青
冯翠苗
李和兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Normal University
University of Shanghai for Science and Technology
Original Assignee
Shanghai Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Normal University filed Critical Shanghai Normal University
Priority to CNB2006101483758A priority Critical patent/CN100540467C/en
Publication of CN100999318A publication Critical patent/CN100999318A/en
Application granted granted Critical
Publication of CN100540467C publication Critical patent/CN100540467C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of new type fluorine functional ordered mesopore carbon material and synthetic method.Synthetic molecular weight is the lower molecular weight fluorine functional resole of 200-500, introduces the tensio-active agent self-assembly system again, induces self-assembly by solvent evaporates; The meso-porous carbon material that has prepared fluorine functional again through carbonization.The meso-porous carbon material high-sequential of prepared fluorine functional, specific surface height (600-1000m 2/ g), the big (0.3-0.7cm of pore volume 3/ g), aperture homogeneous (2.3-5.0nm).In the cyclic voltammetry research of three current potential systems, show, the peak-to-peak potential difference less (Δ E=87mV) of redox of the cyclic voltammetry curve after this material is modified, electrode surface electron transport speed is fast.The present invention compare with traditional fluorination process have simple to operate, advantage such as cost of material is cheap, and equipment requirements is low.Therefore, aspect electrode materials, have wide practical use.

Description

A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof
Technical field
The present invention relates to the material field, be a kind of new type fluorine functional ordered mesopore carbon material and synthetic, the preparation of specifically fluorine-containing fluorine functional resole and utilize the technology of the synthetic fluorine functional meso-porous carbon material of the fluorine-containing resole of this class.
Background technology
In recent years, the synthetic extensive concern that causes people of ordered mesoporous carbon material is because of it has wide practical use in high-tech areas such as absorption, separation, support of the catalyst, electron devices.All the time, the investigator is striving to find a kind of method synthesizing ordered mesoporous carbon material of simple possible.1999, people such as Korea S scientist Ryoo utilize MCM-48 as template, and sucrose is as carbon source, high temperature cabonization under the vitriolic katalysis, remove template silicon with hydrofluoric acid solution or sodium hydroxide solution again, thereby obtain having nano wire, nanometer rod or the nanotube carbon material of array structure.But, the not only time-consuming but also complex procedures of synthesising mesoporous in this way carbon material.People such as Zhao of Fudan University in 2005 east unit are organic precursors with low-molecular-weight resole, and the nonionic triblock copolymer is the ordered mesoporous carbon material that structure directing agent has synthesized aperture homogeneous, bigger serface and pore volume, multiple mesoscopic structure.
Surface-functionalized carbon material has broad prospect of application at aspects such as electrode materials, transmitter, sorbent materials.Therefore, the investigator utilizes the whole bag of tricks that the surface of meso-porous carbon material is modified.Method to the carbon material surface functionalization mainly comprises following several at present: (1) has strong oxidizing property with concentrated nitric acid, ozone etc. oxygenant carries out oxide treatment to carbon material surface; (2) at a certain temperature, the mixed gas with fluorine gas and argon gas purges; (3) carry out functionalization with the diazonium salt or the first imide salt that have aromatic group; (4) carbene or nitrence compounds on carbon surface is modified; (5) reduce processing at carbon material surface with the compound of lithium.But because common carbon material lacks active sites, so its surface-functionalized difficulty, cause these method complex procedures, be difficult to control.
The copolycondensation method is being widely used aspect synthesizing inorganic-organic hybrid silicon materials.This method adopts inorganic silicon and contains the silicon species and the assembling of tensio-active agent cocondensation coalescence of organo-functional group, remove tensio-active agent after, functional group can be evenly distributed in surface, mesopore silicon oxide duct very much, the while can keep the mesoscopic structure of high-sequential.Given this, we utilize organic precursors, phenol and the formaldehyde reaction systematic function resole that contains functional group, and the fluorine functional meso-porous carbon material is synthesized in organic-organic self-assembly further to utilize itself and tensio-active agent to carry out.This fluorine functional ordered mesopore carbon material has the high sight degree of order that is situated between, bigger serface, and the pore size distribution of homogeneous, and aspect electrochemistry, embodied good performance.
Summary of the invention
The objective of the invention is to disclose a kind of fluorine functional resole and novel fluorine ordered mesopore carbon, and simple method for synthesizing.
The lower molecular weight resole of at first synthetic different fluorine content, the main content of controlling fluorine by adjusting phenol and the add-on that contains the organic precursors of fluorine functional group.With the fluorine functional resole as presoma, utilize solvent evaporates to induce the method for self-assembly, fluorine functional resole and nonionogenic tenside carry out organic-synthesising mesoporous high molecular polymer of organic self-assembly again through high temperature cabonization, obtains the ordered mesopore carbon of functionalization.This method has solved the problem of carrying out the functionalization difficulty at carbon material surface, has obtained the aperture homogeneous, the fluorine functional mesoporous carbon of bigger serface high-sequential.
The present invention has synthesized the resole of a series of different fluorine content first.Synthetic method is as follows: at first, with organic precursors---formaldehyde and have the phenols of fluorine functional group and phenol under the katalysis of alkali, aggregate into the fluorine functional resole of different fluorine content under the certain reaction temperature.Reaction transfers to neutrality with pH after finishing, and distillation obtains product.
The used phenols that has the fluorine functional group comprises p-fluorophenol, m fluorophenol, 3,5-difluorophenol etc., and having the phenols of fluorine functional group and the mol ratio of phenol is 0-5, preferred molar ratio is 0-3; The mol ratio of formaldehyde and phenols total amount (phenol and the phenols summation that has the fluorine functional group) is 1.5-3; The used alkaline catalysts of condensation reaction is selected from organic bases such as triethylamine, perhaps one or several in the mineral alkali; The molecular weight of institute's synthetic fluorine functional resole is 200-500; Range of reaction temperature is 60-90 ℃, and the reaction times is 30-60 minute.
Among the present invention, used alkaline catalysts is a sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor, one or more in the triethylamine.Alkaline catalysts adds in the solution with the form of the aqueous solution, and preferred alkaline catalysts is a sodium hydroxide.
Among the present invention, the used phenols that has the fluorine functional group is selected from p-fluorophenol, m fluorophenol, 3, a kind of in the 5-difluorophenol; Be preferably p-fluorophenol.
Among the present invention, the fluorine functional resole is as the precursor of synthesising mesoporous carbon material, and is lower at the initial stage molecular weight of reaction, is 200-500, can well be dissolved in organic solvent.
The present invention is the fluorine-containing ordered mesopore carbon of synthesizing new first.
Synthetic method is as follows: nonionogenic tenside is dissolved in the organic solvent, makes settled solution; The fluorine functional resole organic solution that adds in solution with method for preparing is fully disperseed it then, stirs and makes solvent evaporates induce self-assembly; After treating that solvent evaporates is fully, the low temperature thermosetting, nonionogenic tenside is removed in the high-temperature roasting under reflux extraction or inert atmosphere of gained solid product, handles the highly ordered mesosize pores carbon that obtains fluorine functional through high temperature cabonization again.
The present invention utilizes the volatilization of organic solvent to induce the nonionogenic tenside self-assembly to form the meso-hole structure of high-sequential.Used organic solvent is selected from alcohols, as methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol; The benzene class is as benzene and toluene; Ether, tetrahydrofuran (THF), one or more in chloroform or the methylene dichloride.Be preferably ethanol or ether.
The mass ratio of used fluorine functional resole and tensio-active agent is 1-5, is preferably 1-3.Temperature of reaction is 20-40 ℃; Reaction times is 10 minutes-10 days, 10 minutes-5 hours preferred reaction time.
Used fluorine functional resole organic solution mass concentration ratio is 10%-90%, is preferably 10-60%.
The mass concentration ratio of tensio-active agent organic solution is 2-7%.
It is the fluorine functional ordered mesopore carbon that structure directing agent synthesizes high-sequential that the present invention adopts tensio-active agent.The tensio-active agent that uses is the non-ionic surface tensio-active agent, comprises polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide diblock or triblock copolymer tensio-active agent.Available these general formulas are represented: C aH 2a+1EO b, EO cPO dEO c, EO cBO dEO c, EO cBO d, EO cPO dDeng, wherein a numerical range is 10-18, and b is 5-25, and c is 5-135, and d is 25-135.
Be preferably alkane-polyethylene oxide Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or polyethylene oxide-poly(propylene oxide) triblock copolymer tensio-active agent, as: C aH 2a+1EO b, EO cPO dEO cDeng, wherein a numerical range is 12-18, and b is 5-25, and c is 20-135, and d is 50-135.
Preferred nonionogenic tenside mainly includes Brij56 (C 16H 33EO 10), Brij76 (C 18H 37EO 10), Brij78 (C 16H 33EO 20), P123 (EO 20PO 70EO 20), F127 (EO 106PO 70EO 106), F108 (EO 132PO 50EO 132) etc.Above tensio-active agent can obtain from BASF or Sigma-Aldrich.
Most preferably be F127 (EO 106PO 70EO 106).
The temperature of low temperature thermosetting is 100-120 ℃, and the time is 12-36 hour.
Institute's synthetic mesoporous material removes tensio-active agent among the present invention through reflux extraction or in the rare gas element atmosphere.Reflux extraction removes tensio-active agent can use sulfuric acid, nitric acid or aqueous hydrochloric acid; Can the functional quality mark be the H of 40%-50% 2SO 4Reflux extraction is repeatedly in 80-100 ℃ of water-bath for the aqueous solution.The temperature that roasting removes tensio-active agent is 350-500 ℃, and temperature rise rate is 1-5 ℃/minute.Used rare gas element is nitrogen or argon gas.
Carry out high temperature cabonization afterwards.The temperature of carbonization is 600-900 ℃, carries out in the rare gas element atmosphere; Temperature rise rate is 1-5 ℃/minute.Used rare gas element is nitrogen or argon gas.
The fluorine functional ordered mesopore carbon material of the present invention's preparation has two dimension or three-dimensional mesoscopic structure, and mesoscopic structure is p6mm, Im-3m, Ia-3d; It is bigger also to have specific surface area, the equal first-class characteristics of pore size distribution.The specific surface area of this fluorine functional meso-porous carbon material is 600-1000m 2/ g, pore volume are 0.3-0.7cm 3/ g, the aperture is 2.3-5.0nm.
The fluorine functional meso-porous carbon material of the present invention preparation studies show that in the cyclic voltammetry of three current potential systems: the peak-to-peak potential difference (Δ E=87mV) of the redox of the cyclic voltammetry curve after this material is modified is less, compare with the electrode after modifying with pure mesoporous carbon, its surperficial electron transport speed is fast, and the redox processes that electrode surface takes place is individual process that will definitely be contrary.Therefore, this fluorine function meso-porous carbon material has wide practical use aspect electrode materials.
Fluorine functional ordered mesopore carbon material of the present invention has good characteristic, and preparation method of the present invention compare with traditional fluorine functional process have simple to operate, cheap, advantage such as equipment requirements is easy.
Description of drawings
Fig. 1 has fluorine functional mesoporous carbon characteristic X-ray scattering (SAXS) collection of illustrative plates of two dimension six side p6mm structures.Meso-porous carbon material is made by embodiment 5.
Fig. 2 has the fluorine functional mesoporous carbon feature nitrogen adsorption-desorption isotherm of two dimension six side p6mm structures.Meso-porous carbon material is made by embodiment 5.
Fig. 3 has fluorine functional mesoporous carbon characteristic X-ray scattering (SAXS) collection of illustrative plates of two dimension six side p6mm structures.Make by embodiment 7.
Fig. 4 has the fluorine functional meso-porous carbon material feature nitrogen adsorption-desorption isotherm of two dimension six side p6mm structures.Meso-porous carbon material is made by embodiment 7.
Fig. 5 has feature transmission electron microscope (TEM) figure of mesoporous carbon of the fluorine functional of two dimension six side p6mm structures.Meso-porous carbon material is made by embodiment 7; A and b are the different angles observations.
Fig. 6 has fluorine functional mesoporous carbon characteristic X-ray scattering (SAXS) collection of illustrative plates of three-dimensional cubic Im-3m structure.Meso-porous carbon material is made by embodiment 9.
Fig. 7 has the fluorine functional mesoporous carbon feature nitrogen adsorption-desorption isotherm of three-dimensional cubic Im-3m structure.Meso-porous carbon material is made by embodiment 9.
Fig. 8 has fluorine functional mesoporous carbon characteristic X-ray scattering (SAXS) collection of illustrative plates of three-dimensional cubic Im-3m structure.Meso-porous carbon material is made by embodiment 10.
Fig. 9 has the fluorine functional mesoporous carbon feature nitrogen adsorption-desorption isotherm of three-dimensional cubic Im-3m structure.Meso-porous carbon material is made by embodiment 10.
Figure 10 has feature transmission electron microscope (TEM) figure of the fluorine functional mesoporous carbon of three-dimensional cubic Im-3m structure, and meso-porous carbon material is made by embodiment 10, and a, b and c are respectively the different angles observations.
Electrode that the mesoporous carbon of the two dimension six side p6mm structures of Figure 11 fluorine functional is modified and bare electrode are C-V curve in the electrolytical three-electrode system at the iron potassium hydride KH of 5mmol/L and Klorvess Liquid, and the total number is 20mV/s, and promptly embodiment 11.
Embodiment
Protection scope of the present invention is not limited to embodiment, and for example p-fluorophenol can be with m fluorophenol or 3, and the 5-difluorophenol replaces; Sodium hydroxide solution can use triethylamine, potassium hydroxide, hydrated barta or ammonia soln to replace; Ethanol or ether can use methyl alcohol, n-propyl alcohol, propyl carbinol, tetrahydrofuran (THF), benzene, toluene, chloroform or methylene dichloride to replace; Tensio-active agent F127 (EO 106PO 70EO 106) and Brij76 (C 18H 37EO 10) also can use Brij56 (C 16H 33EO 10), P123 (EO 20PO 70EO 20) or F108 (EO 132PO 50EO 132) replace.Above-mentioned tensio-active agent can obtain from BASF or Sigma-Aldrich.
Embodiment 1
The preparation of novolak resin precursor liquid solution.4g phenol is put in the three-necked flask, and 42 ℃ of heating in water bath make it be transparent liquid; The preparation mass percent is 20% sodium hydroxide solution 1g (take by weighing 0.17g NaOH, add 0.78g distilled water), slowly splashes in this liquid.After 10 minutes, adding quality percentage composition is 37% formaldehyde solution 7.08g, and 70 ℃ were refluxed 1 hour, were cooled to room temperature, regulated pH to neutrality with 2mol/L hydrochloric acid.Underpressure distillation under 45 ℃ of-50 ℃ of conditions, obtaining residue is target product resol.The vacuum tightness of underpressure distillation is 0.0974MPa.After being cooled to room temperature, the ethanol or the diethyl ether solution that are made into mass percentage concentration respectively and are 20%, 50% resol performed polymer are standby.
Embodiment 2
The preparation of fluorine-containing novolak resin precursor liquid solution.3.6g phenol and 0.477g p-fluorophenol are put in the three-necked flask, and 42 ℃ of heating in water bath make it be transparent liquid; The preparation mass percent is 20% sodium hydroxide solution 0.95g (take by weighing 0.17gNaOH, add 0.78g distilled water), slowly splashes in this liquid.After 10 minutes, adding quality percentage composition is 37% formaldehyde solution 7.08g, and 70 ℃ were refluxed 1 hour, were cooled to room temperature, regulated pH to neutrality with 2mol/L hydrochloric acid.Underpressure distillation under 45 ℃ of-50 ℃ of conditions, obtaining residue is the fluorine-containing resol of target product.The vacuum tightness of underpressure distillation is 0.0974MPa.After being cooled to room temperature, the ethanolic soln and the diethyl ether solution that are made into mass percentage concentration respectively and are 20%, 50% fluorine-containing resol performed polymer are standby.
Embodiment 3
The preparation of fluorine-containing novolak resin precursor liquid solution.2.0g phenol and 2.385g p-fluorophenol are put in the three-necked flask, and 42 ℃ of heating in water bath make it be transparent liquid, get mass percent and be 20% sodium hydroxide 0.95g, slowly splash in this liquid.After 10 minutes, adding the quality percentage composition is the formaldehyde solution 7.08g of 37wt.%, and 70 ℃ were refluxed 1 hour, were cooled to room temperature, regulates pH to neutral with 2mol/L hydrochloric acid.Underpressure distillation under 45 ℃ of-50 ℃ of conditions, obtaining residue is the fluorine-containing resol of target product.The vacuum tightness of underpressure distillation is 0.0974MPa.After being cooled to room temperature, the ethanol or the diethyl ether solution that are made into mass percentage concentration respectively and are 20%, 50% fluorine-containing resol performed polymer are standby.
Embodiment 4
The preparation of fluorine-containing novolak resin precursor liquid solution.1.333g phenol and 3.18g p-fluorophenol are put in the three-necked flask, and 42 ℃ of heating in water bath make it be transparent liquid, get mass percent and be 20% sodium hydroxide solution 0.95g, slowly splash in this liquid.After 10 minutes, adding quality percentage composition is 37% formaldehyde solution 7.08g, and 70 ℃ were refluxed 1 hour, were cooled to room temperature, regulated pH to neutrality with 2mol/L hydrochloric acid.Underpressure distillation under 45 ℃ of-50 ℃ of conditions, obtaining residue is the fluorine-containing resol of target product.The vacuum tightness of underpressure distillation is 0.0974MPa.After being cooled to room temperature, the ethanol or the diethyl ether solution that are made into mass percentage concentration respectively and are 20%, 50% fluorine-containing resol performed polymer are standby.
Embodiment 5
Preparation with two dimension six side's mesoscopic structure fluorine functional mesoporous carbon.0.52g F127 is dissolved in the 8g dehydrated alcohol, stirs and got settled solution in 30 minutes.The ethanolic soln 4g of the 20wt.% performed polymer of preparation among the embodiment 2 is joined in the settled solution of above-mentioned F127, mixed 1 hour, evenly be laid on this mixed solution in the culture dish then, room temperature was placed 5 hours, be transferred to the thermosetting of 100 ℃ of baking oven low temperature at last, after 24 hours, with product 350 ℃ of roastings 5 hours under nitrogen atmosphere, 5 ℃/min of temperature rise rate removes tensio-active agent; Continue to be warming up to 900 ℃, 5 ℃/min of temperature rise rate continues 4 hours.The aperture of this material is 2.6nm, and pore volume is 0.53cm 3/ g, specific surface are 750m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of XRD spectra proof gained is p6mm.SAXS and XRD spectra are seen Fig. 1,2.
Embodiment 6
Preparation with two dimension six side's mesoscopic structure fluorine functional mesoporous carbon.0.44g F127 is dissolved in the 16g ether, stirs and obtained settled solution in 30 minutes.The diethyl ether solution 4g of the 50wt.% performed polymer of embodiment 3 preparation is joined in the settled solution of above-mentioned F127, mixed 30 minutes, then this mixed solution evenly is laid in the culture dish, room temperature was placed 5 hours, was transferred to 100 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under nitrogen atmosphere, 3 ℃/min of temperature rise rate removes tensio-active agent, continue to be warming up to 850 ℃, 3 ℃/min of temperature rise rate continues 4 hours.The aperture of this material is 2.8nm, and pore volume is 0.70cm 3/ g, specific surface are 998m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of SAXS spectrogram proof gained is p6mm.
Embodiment 6
Preparation with two dimension six side's mesoscopic structure fluorine functional mesoporous carbon.0.78g Brij 76 is dissolved in the 30g ether, stirs and obtained settled solution in 30 minutes.The diethyl ether solution 4g of the 50wt.% performed polymer of embodiment 3 preparation is joined in the settled solution of above-mentioned Brij 76, mixed 30 minutes, then this mixed solution evenly is laid in the culture dish, room temperature was placed 5 hours, was transferred to 100 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under nitrogen atmosphere, 3 ℃/min of temperature rise rate removes tensio-active agent, continue to be warming up to 850 ℃, 3 ℃/min of temperature rise rate continues 4 hours.The aperture of this material is 2.5nm, and pore volume is 0.60cm 3/ g, specific surface are 760m 2/ g.
Embodiment 7
Preparation with two dimension six side's mesoscopic structure fluorine functional mesoporous carbon.0.44g F127 is dissolved in the 8g ethanol, stirs and obtained settled solution in 30 minutes.The ethanolic soln 4g of the 20wt.% performed polymer of embodiment 3 preparation is joined in the settled solution of above-mentioned F127, mixed 10 minutes, then this mixed solution evenly is laid in the culture dish, room temperature was placed 5 hours, was transferred to 100 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under nitrogen atmosphere, 3 ℃/min of temperature rise rate removes tensio-active agent, continue to be warming up to 900 ℃, 3 ℃/min of temperature rise rate continues 4 hours.The aperture of this material is 2.8nm, and pore volume is 0.70cm 3/ g, specific surface are 998m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of SAXS spectrogram proof gained is p6mm.SAXS and XRD spectra and TEM figure see Fig. 3,4 and 5.
Embodiment 8
Preparation with two dimension six side's mesoscopic structure fluorine functional mesoporous carbon.0.44g F127 is dissolved in the 8g ethanol, stirs and obtained settled solution in 10 minutes.The ethanolic soln 4g of the 20wt.% performed polymer of embodiment 3 preparation is joined in the settled solution of above-mentioned F127, mixed 20 minutes, evenly be laid on this mixed solution in the culture dish then, room temperature was placed 5 hours, be transferred to 120 ℃ of baking ovens at last, carry out the low temperature thermosetting, after 24 hours, with the H of product at 48wt.% 2SO 4Reflux extraction is 24 hours in the aqueous solution, and reflux extraction is 2 times repeatedly, removes tensio-active agent.Further with material under nitrogen atmosphere 900 ℃ the insulation 6 hours, 2 ℃/min of temperature rise rate.The aperture of this material is 4.3nm, and pore volume is 0.47cm 3/ g, specific surface are 567m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of SAXS spectrogram proof gained is p6mm.
Embodiment 9
Preparation with three-dimensional cubic mesoscopic structure fluorine functional mesoporous carbon.0.34g F127 is dissolved in the 8g ethanolic soln, stirs and obtained settled solution in 10 minutes.The ethanolic soln 4g of the 20wt.% performed polymer of embodiment 4 preparation is joined in the settled solution of above-mentioned F127, stirred 20 minutes, evenly be laid on this mixed solution in the culture dish then, room temperature was placed 5 hours, be transferred to 100 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under argon gas atmosphere, 2 ℃/min of temperature rise rate removes tensio-active agent; Continue to be warming up to 600 ℃, 4 ℃/min of temperature rise rate obtained three-dimensional cubic mesoscopic structure fluorine functional mesoporous carbon in lasting 4 hours.The aperture of this material is 2.3nm, and pore volume is 0.43cm 3/ g, specific surface are 741m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of SAXS spectrogram proof gained is Im-3m.SAXS spectrogram and feature nitrogen adsorption-desorption isotherm are seen Fig. 6,7.
Embodiment 10
Preparation with three-dimensional cubic mesoscopic structure fluorine functional mesoporous carbon.0.27g F127 is dissolved in the 8g dehydrated alcohol, stirs and obtained settled solution in 10 minutes.The ethanolic soln 4g of 20% performed polymer of embodiment 4 preparation is joined in the settled solution of above-mentioned F127, stirred 10 minutes, evenly be laid on this mixed solution in the culture dish then, room temperature was placed 5 hours, be transferred to 120 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under argon gas atmosphere, 2 ℃/min of temperature rise rate removes tensio-active agent; Continue to be warming up to 900 ℃, 5 ℃/min of temperature rise rate continues 4 hours.The aperture of this material is 2.6nm, and pore volume is 0.49cm 3/ g, specific surface are 741m 2/ g.The duct spatial symmetry of the meso-porous carbon material of the fluorine functional of SAXS spectrogram proof gained is Im-3m.SAXS spectrogram and feature nitrogen adsorption-desorption isotherm and TEM figure see Fig. 8,9,10.
Embodiment 11
Meso-porous carbon material is applied to adopt cyclic voltammetry in the experiment in the electrochemical analysis test.The fluorine-containing mesoporous carbon 2.6mg of synthetic two dimension six side p6mm structures among the embodiment 4 is dispersed in the dimethyl formamide (DMF) of 1ml, the mesoporous carbon DMF suspension liquid of 20 microlitre 2.6mg/ml is dropped in (φ=3mm), dry stand-by under the infrared lamp on the platinum carbon dioxide process carbon electrode of anticipating.Adopt three-electrode system to measure Fe in the iron cyaniding solution 2+/ Fe3 +The cyclic voltammetry curve of redox processes.Electrochemical workstation be chi660 (CHI, USA), platinum carbon (GC) electrode, platinum electrode, saturated calomel electrode are respectively as working electrode, counter electrode and reference electrode in the three-electrode system, sweep voltage is-0.2～0.7V, the concentration of iron cyaniding solution is 5mMK 4Fe (CN) 6-KCl the aqueous solution, the total number are 20mv/s.The C-V curve is seen Figure 11, obtains Δ E=87mV from the C-V curve calculation.

Claims (17)

1. the preparation method of a fluorine functional ordered mesopore carbon material, it is characterized in that, comprise the steps: respectively tensio-active agent and lower molecular weight fluorine functional resole to be dissolved in organic solvent, these two kinds of organic solutions are mixed, stir and make its solvent evaporates induce self-assembly; After treating that solvent evaporates fully, 100-120 ℃ of following low temperature thermosetting 12-36 hour; Remove tensio-active agent, carbonization promptly obtains the fluorine-containing meso-porous carbon material of high-sequential functionalization;
Described fluorine functional resole, molecular weight are 200-500;
The mass ratio of described fluorine functional resole and tensio-active agent is 1-5;
Described tensio-active agent is a nonionogenic tenside, is polyethylene oxide-poly(propylene oxide) triblock copolymer or alkane-polyethylene oxide Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock tensio-active agent, and its general formula can be used C aH 2a+1EO b, EO cPO dEO cExpression, wherein a numerical range is 10-18, and b is 5-25, and c is 5-135, and d is 25-135;
Described organic solvent is alcohols, benzene, toluene, tetrahydrofuran (THF), chloroform, methylene dichloride or the ether of C1-C4;
The preparation method of described lower molecular weight fluorine functional resole may further comprise the steps:
Have the phenols of fluorine functional group and formaldehyde as organic precursors, with phenol under the katalysis of alkali, under 60-90 ℃, carry out condensation reaction, the reaction times of condensation is 30-60 minute;
Described alkali is selected from a kind of in triethylamine, sodium hydroxide, potassium hydroxide, hydrated barta, the ammoniacal liquor;
The described phenols that has the fluorine functional group is selected from p-fluorophenol, m fluorophenol, 3, a kind of in the 5-difluorophenol;
Describedly have the phenols of fluorine functional group and the mol ratio of phenol is 0-5;
Described formaldehyde and phenol are 1.5-3 with the mol ratio that has the phenols summation of fluorine functional group.
2. the preparation method of claim 1 is characterized in that, described organic solvent is ethanol or ether.
3. the preparation method of claim 1 is characterized in that, described tensio-active agent is C 16H 33EO 10, C 16H 33EO 20, C 18H 37EO 10, EO 20PO 70EO 20, EO 106PO 70EO 106, EO 132PO 50EO 132In one or more.
4. the preparation method of claim 3 is characterized in that, described tensio-active agent is EO 106PO 70EO 106Or C 18H 37EO 10
5. the preparation method of claim 1 is characterized in that, the mass ratio of described fluorine functional resole and tensio-active agent is 1-3.
6. the preparation method of claim 1 is characterized in that, after tensio-active agent organic solution and fluorine functional resole organic solution were mixed, temperature of reaction was 20-40 ℃, and the reaction times is 10 minutes-10 days.
7. the preparation method of claim 6 is characterized in that, after tensio-active agent organic solution and fluorine functional resole organic solution mixed, the reaction times was 10 minutes-5 hours.
8. the preparation method of claim 1 is characterized in that, described fluorine functional resole organic solution quality is 10%-90% than concentration.
9. the preparation method of claim 1 is characterized in that, described tensio-active agent organic solution quality is 2-7% than concentration.
10. the preparation method of claim 1 is characterized in that, the method for removing tensio-active agent is to remove tensio-active agent with sulfuric acid, nitric acid or hydrochloric acid soln reflux extraction; Perhaps tensio-active agent is removed in roasting in the rare gas element atmosphere, and maturing temperature is 350-500 ℃.
11. the preparation method of claim 2 is characterized in that, carbonization is carried out in the rare gas element atmosphere, and temperature is 600-900 ℃.
12. the preparation method of claim 10 or 11 is characterized in that, described rare gas element is nitrogen or argon gas.
13. the preparation method of claim 10 or 11 is characterized in that, the temperature rise rate when described roasting or carbonization is 1-5 ℃/minute.
14. the preparation method of claim 1 is characterized in that, describedly has the phenols of fluorine functional group and the mol ratio of phenol is 0-3.
15. the preparation method of claim 1 is characterized in that, the described phenols that has the fluorine functional group is a p-fluorophenol.
16. the preparation method of claim 1 is characterized in that, described alkali is sodium hydroxide.
17. a fluorine functional ordered mesopore carbon material is characterized in that, by the described preparation method's preparation of claim 1～16.
CNB2006101483758A 2006-12-29 2006-12-29 A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof Expired - Fee Related CN100540467C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006101483758A CN100540467C (en) 2006-12-29 2006-12-29 A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006101483758A CN100540467C (en) 2006-12-29 2006-12-29 A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof

Publications (2)

Publication Number Publication Date
CN100999318A CN100999318A (en) 2007-07-18
CN100540467C true CN100540467C (en) 2009-09-16

Family

ID=38258160

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006101483758A Expired - Fee Related CN100540467C (en) 2006-12-29 2006-12-29 A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof

Country Status (1)

Country Link
CN (1) CN100540467C (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101455983B (en) * 2008-12-30 2011-01-12 上海师范大学 Preparation method of PPh2-ordered mesopore polymer-Pd(II) heterogeneous catalyst and use thereof
CN105742655B (en) * 2014-12-11 2018-11-02 中国科学院大连化学物理研究所 A kind of classifying porous carbon material of fuel cell and its preparation and application
CN107251275A (en) * 2015-02-19 2017-10-13 株式会社理光 Nonaqueous electrolytic solution charge storage element
CN105566589B (en) * 2015-12-08 2017-11-07 上海师范大学 Amino functional ordered mesoporous phenolic resin material and preparation method thereof
CN106082165B (en) * 2016-06-12 2018-06-01 太原理工大学 The preparation method of micro- composite mesoporous carbon material
CN113603077A (en) * 2021-08-23 2021-11-05 绍兴海崐新材料科技有限公司 Preparation method of high-adsorption-force spherical mesoporous carbon

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ordered Mesoporous Polymers and Homologous CarbonFrameworks Amphiphilic Surfactant Templating and DirectTransformation. Yan Meng, Dong Gu, Fuqiang Zhang, et al.Angew. Chem. Int. Ed.,Vol.44 No.43. 2005
Ordered Mesoporous Polymers and Homologous CarbonFrameworks Amphiphilic Surfactant Templating and DirectTransformation. Yan Meng, Dong Gu, Fuqiang Zhang, et al.Angew. Chem. Int. Ed.,Vol.44 No.43. 2005 *

Also Published As

Publication number Publication date
CN100999318A (en) 2007-07-18

Similar Documents

Publication Publication Date Title
CN100540467C (en) A kind of new type fluorine functional ordered mesopore carbon material and synthetic method thereof
Zhao et al. Sulphur-doped carbon nanosheets derived from biomass as high-performance anode materials for sodium-ion batteries
Zhou et al. Polyaniline-encapsulated silicon on three-dimensional carbon nanotubes foam with enhanced electrochemical performance for lithium-ion batteries
CN100469692C (en) Nitrogen-containing ordered mesopore carbon and its synthesis method
Wu et al. Organically modified silica-supported ionogels electrolyte for high temperature lithium-ion batteries
CN103517912B (en) Sulfonates compound, the polymer dielectric film comprising the compound and the fuel cell comprising the polymer dielectric film
WO2017190677A1 (en) Method for preparing boron-doped porous carbon sphere
Niu et al. Hierarchical core–shell heterostructure of porous carbon nanofiber@ ZnCo 2 O 4 nanoneedle arrays: advanced binder-free electrodes for all-solid-state supercapacitors
Huang et al. Multi-protection from nanochannels and graphene of SnSb-graphene‑carbon composites ensuring high properties for potassium-ion batteries
Salunkhe et al. Fabrication of symmetric supercapacitors based on MOF-derived nanoporous carbons
US7824646B2 (en) Carbon and carbon composites with highly ordered mesosize pores
Song et al. Porous nano-Si/carbon derived from zeolitic imidazolate frameworks@ nano-Si as anode materials for lithium-ion batteries
CN102101665A (en) Method for preparing nickeliferous ordered mesoporous carbon material by one-step method
CN102977397B (en) Preparation method of ordered mesoporous resorcinol-formaldehyde resin and mesoporous carbon
CN110323072B (en) Preparation method of nitrogen-doped hollow carbon sphere/MOF-based porous carbon composite material applied to supercapacitor
CN109796016A (en) A method of regulation MXene nanoscale twins spacing
Wang et al. Novel activated N-doped hollow microporous carbon nanospheres from pyrrole-based hyper-crosslinking polystyrene for supercapacitors
CN108940264A (en) A kind of Mn/Ce base catalyst and preparation method thereof with room temperature decomposing formaldehyde performance
KR20100125798A (en) Composition for mesoporous carbon which can control the pore size and its production method
CN103157467A (en) Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis
CN109879268B (en) Carbon hollow sphere composite material and preparation method and application thereof
CN106517227A (en) Microwave method for rapidly preparing short-rod-like SBA-15
CN100577271C (en) Method for preparing organic-inorganic hybridization anion exchange membrane based on co-polymer
CN110002429B (en) Carbon nanotube/transition metal hydroxide composite electrode material and preparation method thereof
Schnucklake et al. Porous carbon–carbon composite electrodes for vanadium redox flow batteries synthesized by twin polymerization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090916

Termination date: 20151229

EXPY Termination of patent right or utility model