CN103274387A - Method for preparing mesoporous carbon nanofibers (MCFs) - Google Patents
Method for preparing mesoporous carbon nanofibers (MCFs) Download PDFInfo
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- CN103274387A CN103274387A CN2013102136711A CN201310213671A CN103274387A CN 103274387 A CN103274387 A CN 103274387A CN 2013102136711 A CN2013102136711 A CN 2013102136711A CN 201310213671 A CN201310213671 A CN 201310213671A CN 103274387 A CN103274387 A CN 103274387A
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Abstract
The invention discloses a method for preparing mesoporous carbon nanofibers (MCFs). The method comprises the steps of mixing an aqueous solution of tin, modified by citric acid, with polyvinyl alcohol so as to obtain a mixture serving as electrospinning liquid, drying composite fibers obtained through electrostatic spinning, carrying out oxygen-free heat treatment on the composite fibers in a tubular furnace, soaking the fibers in concentrated hydrochloric acid, and finally, repeatedly washing, thereby obtaining the MCFs. According to the method, the preparation process is simple, and the prepared products can be applied to catalyst carriers and electrode materials of electric double-layer capacitors.
Description
Technical field
The present invention relates to the preparation of porous material, particularly a kind of preparation method of mesoporous carbon nanofiber.
Background technology
Mesoporous carbon is the novel non-silicon-based mesoporous material of a class of recent findings, because it has huge surface-area and pore volume, be expected to very much obtain important use at aspects such as support of the catalyst, electrode materials, hydrogen storage materials, therefore be subjected to paying much attention to (J.Mater.Chem., 2004,14,478).Electrode materials and double layer capacitor that meso-porous carbon material is widely used in battery because of its regular pore passage structure and bigger pore capacities and excellent conducting performance.Porous carbon with meso-hole structure has short relatively the evolving path can make things convenient for the transmission of guest molecule, and therefore this carbon material has tangible effect to the mass transfer problem that raising reaction efficiency, solution diffusional resistance cause too greatly.Mesoporous carbon has pore size distribution preferably, mean pore size is greater than 2nm, for the orderly mesoporous carbon of duct queueing discipline, electrolyte ion can be done locomotory movement freely in hole, can form electrostatic double layer fast, therefore have stronger charge and discharge ability, and demonstrate excellent electric double layer capacitance performance.Characteristics such as mesoporous carbon is big because of its specific surface area, pore size distribution is moderate, electroconductibility is good become the ideal electrode material of double layer capacitor.The preparation method commonly used of meso-porous carbon material comprises: chemical activation method (Micropor.Mater., 1995,3,603), catalytic activation method (Carbon, 2012,50,2824), sol-gel method (Langmuir, 1996,12,6167), mesoporous silicon template (Applied Energy, 2012,100,66) and surfactant templates method (Chem.Soc.Rev., 2011,40,3854) etc.The continuity of carbon nanofiber and distinctive accumulation pore structure thereof not only are conducive to the storage (Carbon, 2013,290) of electrolytical diffusion and electric charge in the double layer capacitor; And this special structure of carbon nanofiber also is conducive to catalyst particle and is dispersed on the fiber better, thereby forming good continuous conduction structure makes catalyzer have less charge-transfer resistance when catalytic oxidation, raising (the J Power Sources that is conducive to catalyst performance more, 2011,7973).Therefore, preparation a kind of combine mesoporous carbon and carbon nanofiber separately the new carbon of advantage and characteristics have very important meaning for double layer capacitor and support of the catalyst.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of mesoporous carbon nanofiber, the mesoporous carbon nanofiber that this method prepares has characteristics such as specific surface area is big, pore size distribution is moderate, conductivity is good.
The preparation method of a kind of mesoporous carbon nanofiber provided by the invention comprises the steps:
1) method of electrostatic spinning prepares conjugated fibre
Be 50～150mg/mL SnCl to concentration
45H
2Dripping strong aqua in the aqueous solution of O, make it to precipitate fully, is in the citric acid solution of 200mg/mL with resolution of precipitate in concentration afterwards, V
SnCl45H2O/ V
Citric acid solution=1 ︰ 0.5 obtains containing the precursor solution of tin, and the precursor solution that contains tin in the every 1mL ratio that adds the 100mg polyvinyl alcohol is mixed with electrospinning solution at last, carries out electrostatic spinning then and obtains conjugated fibre;
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1000～1200 ℃ were heated 1～3 hour in inert atmosphere; Conjugated fibre after the thermal treatment is dipped in concentrated hydrochloric acid does not have bubble to produce, and is washed with distilled water to pH=6～7, and oven dry obtains mesoporous carbon nanofiber (MCFs).
V in the step 1)
SnCl45H2O/ V
NH3H2O=1 ︰ 0.05～0.3.
The mesoporous carbon nanofiber that the present invention prepares can be used for the electrode materials of support of the catalyst and double layer capacitor.Can increase substantially activity, stability and the anti-poisoning capability of catalyst oxidation methyl alcohol as support of the catalyst; As the electrode materials of double layer capacitor, because it has the higher requirement that can satisfy the double layer capacitor fast charging and discharging than electric capacity and chemical stability.
Compared with prior art, advantage of the present invention: (1) does not need silicon template and surfactant templates, can directly obtain the mesoporous carbon nanofiber by metal etch; (2) can prepare different pore sizes, the mesoporous carbon nanofiber of different specific surface areas by the content of controlling the tin element that adds; (3) the pore size distribution homogeneous that obtains than existing catalytic activation method of Zhi Bei material; (4) the mesoporous carbon nanofiber specific surface area that obtains is big, and good conductivity can be used as the electrode of support of the catalyst and double layer capacitor; (5) provide in the mesoporous novel method of carbon nanofiber manufacturing, for carbon nanofiber provides new potential utility value; (6) this method preparation process is simple, easy to operate, and cheapness meets the characteristics of batch process.
Description of drawings
Fig. 1 is the SEM figure of the mesoporous carbon nanofiber (MCFs) among the embodiment 1.
Fig. 2 is the TEM figure of the mesoporous carbon nanofiber (MCFs) among the embodiment 2.
Fig. 3 is the isothermal nitrogen adsorption desorption graphic representation of the mesoporous carbon nanofiber (MCFs) among the embodiment 3.
Fig. 4 is the pore size distribution curve of the mesoporous carbon nanofiber (MCFs) among the embodiment 4.
Fig. 5 is to be the catalytic oxidation methanol loop volt-ampere curve of the synthetic Pt-MCFs-60% catalyzer of carrier with the mesoporous carbon nanofiber among the embodiment 5.
Fig. 6 for the mesoporous carbon nanofiber among the embodiment 5 be the synthetic Pt-MCFs-60% catalyzer of carrier under the constant voltage of 0.45V, the timing ampere curve of catalytic oxidation methyl alcohol.
Fig. 7 is as electrode, at 100mV s with the mesoporous carbon nanofiber among the embodiment 6
-1Sweep speed under the CV graphic representation.
Fig. 8 is as electrode, at 2000mV s with the mesoporous carbon nanofiber among the embodiment 6
-1Sweep speed under the CV graphic representation.
Embodiment
Embodiment 1
1) method of electrostatic spinning prepares conjugated fibre
With 1g SnCl
45H
2O is dissolved in the solution that is mixed with 50mg/mL in the 20mL deionized water, drips the 2mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre; The electrostatic spinning voltage control is at 12～15kV.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1000 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).As shown in Figure 1, we find that the nanofiber surface is very coarse, and there is the hole about many diameter 5nm the inside of fiber.
1) method of electrostatic spinning prepares conjugated fibre
With 2g SnCl
45H
2O is dissolved in the solution that is mixed with 100mg/mL in the 20mL deionized water, drips the 4mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1000 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).As shown in Figure 2, we find that fibrous inside has the hole about the internal diameter 5nm of many mutual perforations.
1) method of electrostatic spinning prepares conjugated fibre
With 3g SnCl
45H
2O is dissolved in the solution that is mixed with 150mg/mL in the 20mL deionized water, drips the 6mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1000 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).As shown in Figure 3, we find that this mesoporous material presents typical the 4th class winding, and the desorption curve sharply descends under 0.4～0.5 relative pressure, and above phenomenon illustrates that this material has the hole that distribution is quite concentrated.Test result draws this material specific surface area up to 800m in addition
2g
-1
Embodiment 4
1) method of electrostatic spinning prepares conjugated fibre
With 1g SnCl
45H
2O is dissolved in the solution that is mixed with 50mg/mL in the 20mL deionized water, drips the 2mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1200 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).As shown in Figure 4, we find that this material is typical mesoporous material.According to the isothermal adsorption curve, and calculate mean pore size by the BJH method and be approximately 11.3nm.The mean pore size that obtains exporting according to the desorption curve is approximately 4.4nm, and the pore size distribution range of outlet narrow a lot of than fibrous inside.
1) method of electrostatic spinning prepares conjugated fibre
With 2g SnCl
45H
2O is dissolved in the solution that is mixed with 100mg/mL in the 20mL deionized water, drips the 4mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1200 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).The catalyst performance test condition is: working electrode Pt-MCFs-60%; The loading of catalyzer is: 0.21mg/cm
-2Counter electrode: platinum electrode; Reference electrode: saturated calomel electrode (SCE); Electrolytic solution: N
2Saturated 0.5molL
-1H
2SO
4+ 1.0molL
-1CH
3OH solution; Potential scanning speed=50mVs
-1Working temperature: 25 ℃.As shown in Figure 5, the peak current density If maximum value of He Cheng catalyst oxidation methyl alcohol is 65.7mA/cm
-2, I
f/ I
bValue is 0.99.These data declarations, Pt-MCFs-60% electrode catalytic oxidation methyl alcohol active high and intermediate products such as further oxidation CO have been played certain effect.As shown in Figure 6, reaching maximum value 27.4mA/cm
-2After, current density has presented a process that continues to descend along with the prolongation of sweep time.After the scanning 10000s, the current density of electrode Pt-MCFs-60% catalyzed oxidation methyl alcohol drops to 9.3mAcm
-2, reduced by 65.4%.
Embodiment 6
1) method of electrostatic spinning prepares conjugated fibre
With 3g SnCl
45H
2O is dissolved in the solution that is mixed with 150mg/mL in the 20mL deionized water, drips the 6mL strong aqua then and makes it to precipitate fully.Afterwards precipitation being transferred to 10mL concentration is in the 200mg/mL citric acid solution, and ultrasonic and heating is dissolved precipitation fully.At last polyvinyl alcohol and the precursor solution that contains tin are mixed with electrospinning solution in the ratio of 140mg PVA/1400 μ L precursor solution and carry out electrostatic spinning, obtain conjugated fibre.
2) metal etch of carbon nanofiber
The conjugated fibre of drying is transferred in the tube furnace, and 1200 ℃ are heated 2h down in inert atmosphere.Fiber after the thermal treatment is soaked in the concentrated hydrochloric acid of capacity, repeatedly washing by soaking.At last the sample oven dry is obtained mesoporous carbon nanofiber (MCFs).The test condition of capacitive property is: working electrode: MCFs; Electrolytic solution: 6M KOH; Potential scanning speed: 5to2000mVs
-1Voltage window :-0.75to+0.75V; Working temperature: 25 ℃.As shown in Figure 7, even at 100mV s
-1Sweep speed down the CV curve still present good rectangle, illustrate that this material has good electric double layer capacitance, 5mV s
-1Sweep speed under the ratio capacitance up to 105.9F g
-1As shown in Figure 8, when sweeping speed up to 2000mv s
-1The time, the distortion that becomes of CV curve, this is owing to sweep at height that ionogen increase of diffusion resistance in mesoporous causes under the speed, is 58.1F g than capacitance at this moment
-1
Claims (2)
1. the preparation method of a mesoporous carbon nanofiber is characterized in that, comprises the steps:
1) be 50～150mg/mL SnCl to concentration
45H
2Dripping strong aqua in the aqueous solution of O, make it to precipitate fully, is in the citric acid solution of 200mg/mL with resolution of precipitate in concentration afterwards, V
SnCl45H2O/ V
Citric acid solution=1 ︰ 0.5 obtains containing the precursor solution of tin, and the precursor solution that contains tin in the every 1mL ratio that adds the 100mg polyvinyl alcohol is mixed with electrospinning solution at last, carries out electrostatic spinning then and obtains conjugated fibre;
2) conjugated fibre of drying is transferred in the tube furnace, 1000～1200 ℃ were heated 1～3 hour in inert atmosphere; Conjugated fibre after the thermal treatment is dipped in concentrated hydrochloric acid does not have bubble to produce, and is washed with distilled water to pH=6～7, and oven dry obtains mesoporous carbon nanofiber (MCFs).
2. the preparation method of a kind of mesoporous carbon nanofiber as claimed in claim 1 is characterized in that, V in the described step 1)
SnCl45H2O/ V
NH3H2O=1 ︰ 0.05～0.3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772791A (en) * | 2021-09-15 | 2021-12-10 | 山东省科学院新材料研究所 | Self-supporting porous carbon fiber material and preparation method and application thereof |
| CN113817450A (en) * | 2021-09-30 | 2021-12-21 | 国网河北省电力有限公司电力科学研究院 | Phase-change heat storage material for heating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859896A (en) * | 2010-05-21 | 2010-10-13 | 北京化工大学 | Preparation method of tin/carbon composite nano fiber film cathode material |
| US20110171565A1 (en) * | 2006-06-13 | 2011-07-14 | Sabanci Universitesi At Orhanli | Carbon nanofibers containing catalyst nanoparticles |
| CN102838094A (en) * | 2012-09-21 | 2012-12-26 | 北京博电新力电气股份有限公司 | Preparation method of silver-doped nano tin dioxide powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110171565A1 (en) * | 2006-06-13 | 2011-07-14 | Sabanci Universitesi At Orhanli | Carbon nanofibers containing catalyst nanoparticles |
| CN101859896A (en) * | 2010-05-21 | 2010-10-13 | 北京化工大学 | Preparation method of tin/carbon composite nano fiber film cathode material |
| CN102838094A (en) * | 2012-09-21 | 2012-12-26 | 北京博电新力电气股份有限公司 | Preparation method of silver-doped nano tin dioxide powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772791A (en) * | 2021-09-15 | 2021-12-10 | 山东省科学院新材料研究所 | Self-supporting porous carbon fiber material and preparation method and application thereof |
| CN113817450A (en) * | 2021-09-30 | 2021-12-21 | 国网河北省电力有限公司电力科学研究院 | Phase-change heat storage material for heating and preparation method thereof |
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