CN104372434A - Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production - Google Patents
Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production Download PDFInfo
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- CN104372434A CN104372434A CN201410646182.XA CN201410646182A CN104372434A CN 104372434 A CN104372434 A CN 104372434A CN 201410646182 A CN201410646182 A CN 201410646182A CN 104372434 A CN104372434 A CN 104372434A
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- pan
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- composite nano
- cocl2
- nano fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a preparation method of PAN/CoCl2/CNTs composite nano fibers and application of the PAN/CoCl2/CNTs composite nano fibers. Carbon nano tubes (CNTs) and cobalt chloride hexahydrate (CoCl2.6H2O) are simultaneously doped into polyacrylonitrile (PAN) nano fibers. The doping ratio of the CNTs to the CoCl2.6H2O is adjusted so that the PAN nano fibers have high strength and high conductive performance. The prepared composite nano fibers can be used as a catalyst for hydrolyzing the NaBH4 to produce hydrogen. A research shows that the composite nano fiber material has a stable structure and is suitable for catalyzing the NaBH4 to produce the hydrogen, and can be repeatedly utilized.
Description
Technical field
The present invention relates to a kind of composite nano-fiber material, be specifically related to a kind of PAN and adulterate CoCl simultaneously
2with the preparation method of the PAN/CoCl2/CNTs composite nano fiber of CNTs and at NaBH
4application in hydrogen manufacturing.
Background technology
Along with the fast development of economy, people are also increasing day by day to the demand of the energy.When fossil energy is precarious, the exploitation of novel energy are particularly important.Hydrogen Energy is the one in numerous clean energy resource, has attracted increasing concern, and therefore the research of hydrogen storage material also becomes a popular topic now.NaBH in all hydrogen storage materials
4due to itself is nontoxic, hydrogen storage content is large, hydrogen purity is high, accumulating is convenient and accessory substance kodalk also environmental sound receive the extensive concern of people.NaBH
4exothermic reaction can occur in water, reaction equation is as follows: NaBH
4+ 2H
2o=NaBO
2+ 4H
2Δ H=-300kJ/mol (1)
In order to improve NaBH
4hydrogen-producing speed, a lot of catalyst can be used for accelerating hydrolyzing N aBH
4.Some noble metals such as Pt and Ru can be used as catalyst and efficiency is very high, but expensively cannot widely use.Recent CoB powder is widely studied in NaBH4 hydrolytic hydrogen production.Although CoB is at catalyzing N aBH
4activity in hydrolytic hydrogen production is very high, but easily assembles due to pulverous CoB and be difficult to again reuse, and therefore some load type Cos B catalyst application is more extensive, such as CoB/SiO
2, CoB/C, CoB/CNTs etc.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art part, a kind of preparation method of PAN/CoCl2/CNTs composite nano fiber is provided, solve the problem of low, the not reproducible utilization of catalytic efficiency in prior art.
Another object of the present invention is to provide a kind of PAN/CoCl2/CNTs composite nano fiber at NaBH
4application in hydrogen manufacturing.
For achieving the above object, preparation method of the present invention comprises the steps:
Step 1, get the CNTs after purifying and add organic solvent for ultrasonic vibration 1-3h, the mass ratio of CNTs and organic solvent is 0.05-1:28, then 2-4h is stirred until CNTs evenly spreads in organic solvent, form aaerosol solution A, high molecular polymer PAN is joined in above-mentioned aaerosol solution A the formation mixed liquid B that stirs, the mass ratio of high molecular polymer PAN and aaerosol solution A is 2:20-40; To be added in cobalt source in above-mentioned mixed liquid B and Keep agitation obtains electrostatic spinning precursor solution C, the mass ratio of cobalt source and mixed liquid B is 0.4:25-45;
Step 2, is placed in plastic injector electrostatic spinning by obtained precursor solution C, is connected to by high-voltage anode on the Metallic Nozzle At The Ingot of syringe tip; Negative electrode is connected as receiving terminal with aluminium foil, and at two interpolar high-pressure direct currents; Fixing distance between syringe nozzle and aluminium foil receiver; On aluminium foil, one deck fibrofelt is formed in electrostatic spinning process; Fibrofelt is collected and is placed on drying in vacuum drying oven, obtain target product PAN/CoCl
2/ CNTs composite nanometer fiber felt.
In described step 1, the purification step of CNTs is: CNTs is placed in container, adds 69wt% red fuming nitric acid (RFNA) under room temperature, and the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:70-200, magnetic agitation 10-30min; Then be placed in 120-160oC oil bath and stir constant temperature 24-48h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 50-70oC.
Cobalt source in described step 1 is cobalt chloride, cobalt nitrate, cobaltous sulfate or organic acid cobalt salt.
The organic solvent of described step 1 is DMF, ethanol or both mixed solutions.
Electrospinning conditions in described step 2 is: voltage is 20kV, and the distance between syringe nozzle and aluminium foil receiver is 15cm, and syringe flow velocity is 1.0ml/h.
The aluminium foil receiver adopted in described step 2 is high-speed rotary rotary drum receiver, and rotating speed is 500 turns/min.
In described step 2, fibrofelt is in vacuum drying oven 50
oc vacuumize 12h.
PAN/CoCl2/CNTs composite nano fiber is at NaBH
4application in hydrogen manufacturing.
PAN/CoCl
2/ CNTs composite nano fiber catalyzing N aBH
4the reaction condition of hydrogen manufacturing is 15
oc, 25
oc, 35
oc or 45
oc; Reuse 5 times.
Advantageous effect of the present invention is as follows:
By the enforcement of technical solution of the present invention, can be good at being applied to preparing hydrogen by sodium borohydride hydrolysis, process simplification, equipment are reduced, and more than 5 times can be reused occupy greater advantages economically.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
Fig. 1 is PAN/CoCl of the present invention
2/ CNTs composite nano fiber catalyst S EM schemes;
Fig. 2 a-Fig. 2 d is the PAN/CoCl of the different CNTs content of the present invention
2/ CNTs composite nano fiber catalyst TEM schemes;
Fig. 3 is the PAN/CoCl of the different CNTs content of the present invention
2/ CNTs composite nano fiber catalyst preparing hydrogen by sodium borohydride hydrolysis rate diagram.
Detailed description of the invention
Water used in following example is deionized water; Agents useful for same, except special instruction, all adopts AR; In embodiment, obtained PAN/CoCl
2the SEM picture of/CNTs composite nano fiber catalyst is scanned by Hitachi S-3500N ESEM and obtains; Transmission electron microscope is used for have studied CNTs at PAN/CoCl in the present invention
2the distribution situation of/CNTs composite nano fiber inside.
embodiment 1
The electrostatic spinning solution of configuration containing 4.0%CNTs, then prepares composite nano fiber by electrostatic spinning technique.Concrete steps are as follows:
Get the CNTs0.08g after purifying and add sonic oscillation 1h in 28.0gDMF, then stir 2h until CNTs evenly spreads in DMF.Next, in above-mentioned solution, 2.0g polyacrylonitrile (PAN) is added.Finally add 0.4gCoCl2 and Keep agitation 48h.
Above-mentioned solution is placed in 10ml injector for medical purpose and carries out electrostatic spinning.The voltage of electrostatic spinning is 20kV, and the distance between shower nozzle and aluminium foil receiver is 15cm, and the flow control of precursor solution is 1.0ml/h.Aluminium foil receiver is high-speed rotary rotary drum receiver, and rotating speed is 500 turns/min.
Obtained composite nano fiber is joined the NaBH that 50ml mass concentration is 1.0%
4in the device of hydrolytic hydrogen production.Unit temp controls 25
oc is hydrolyzed hydrogen production reaction, and reaction rate is 1162.3 ml/min/g.
embodiment 2
The electrostatic spinning solution of configuration containing 8.0%CNTs, then prepares composite nano fiber by electrostatic spinning technique.Concrete steps are as follows:
Get the CNTs0.16g after purifying and add sonic oscillation 1h in 28.0gDMF, then stir 2h until CNTs evenly spreads in DMF.Next, in above-mentioned solution, 2.0gPAN is added.Finally add 0.4gCoCl2 and Keep agitation 48h.
Above-mentioned solution is placed in 10ml injector for medical purpose and carries out electrostatic spinning.The voltage of electrostatic spinning is 20kV, and the distance between shower nozzle and receiver is 15cm, and the flow control of precursor solution is 1.0ml/h.
Obtained composite nano fiber is joined the NaBH that 50ml mass concentration is 1.0%
4in the device of hydrolytic hydrogen production.Unit temp controls 25
oc is hydrolyzed hydrogen production reaction, and reaction rate is 1169.4 ml/min/g.
embodiment 3
The electrostatic spinning solution of configuration containing 10.0%CNTs, then prepares composite nano fiber by electrostatic spinning technique.Concrete steps are as follows:
Get the CNTs0.20g after purifying and add sonic oscillation 1h in 28.0gDMF, then stir 2h until CNTs evenly spreads in DMF.Next, in above-mentioned solution, 2.0gPAN is added.Finally add 0.4gCoCl2 and Keep agitation 48h.
Above-mentioned solution is placed in 10ml injector for medical purpose and carries out electrostatic spinning.The voltage of electrostatic spinning is 20kV, and the distance between shower nozzle and receiver is 15cm, and the flow control of precursor solution is 1.0ml/h.
Obtained composite nano fiber is joined the NaBH that 50ml mass concentration is 1.0%
4in the device of hydrolytic hydrogen production.Unit temp controls 25
oc is hydrolyzed hydrogen production reaction, and reaction rate is 1179.2 ml/min/g.
embodiment 4
The electrostatic spinning solution of configuration containing 12.0%CNTs, then prepares composite nano fiber by electrostatic spinning technique.Concrete steps are as follows:
Get the CNTs0.24g after purifying and add sonic oscillation 1h in 28.0gDMF, then stir 2h until CNTs evenly spreads in DMF.Next, in above-mentioned solution, 2.0gPAN is added.Finally add 0.4gCoCl2 and Keep agitation 48h.
Above-mentioned solution is placed in 10ml injector for medical purpose and carries out electrostatic spinning.The voltage of electrostatic spinning is 20kV, and the distance between shower nozzle and receiver is 15cm, and the flow control of precursor solution is 1.0ml/h.
Obtained composite nano fiber is joined the NaBH that 50ml mass concentration is 1.0%
4in the device of hydrolytic hydrogen production.Unit temp controls 25
oc is hydrolyzed hydrogen production reaction, and reaction rate is 1255.1 ml/min/g.
embodiment 5
The purification process of CNTs: CNTs is placed in container, adds 69wt% red fuming nitric acid (RFNA) under room temperature, the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:70, magnetic agitation 10min; Then be placed in 120oC oil bath and stir constant temperature 24h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 50oC.
Get the CNTs after purifying and add sonic oscillation 3h in organic solvent ethanol, the mass ratio of CNTs and organic solvent ethanol is 0.05:28, then 2h is stirred until CNTs evenly spreads in organic solvent ethanol, form aaerosol solution A, high molecular polymer PAN is joined in above-mentioned aaerosol solution A the formation mixed liquid B that stirs, the mass ratio of high molecular polymer PAN and aaerosol solution A is 2:20; To be added by cobalt nitrate in above-mentioned mixed liquid B and Keep agitation obtains electrostatic spinning precursor solution C, the mass ratio of cobalt source and mixed liquid B is 0.4:25; Other step is with embodiment 1.
embodiment 6
The purification step of CNTs is: CNTs is placed in container, adds 69wt% red fuming nitric acid (RFNA) under room temperature, and the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:200, magnetic agitation 30min; Then be placed in 160oC oil bath and stir constant temperature 48h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 70oC;
Get the CNTs after purifying and add sonic oscillation 3h in organic solvent DMF, the mass ratio of CNTs and organic solvent DMF is 1:28, then 3h is stirred until CNTs evenly spreads in organic solvent, form aaerosol solution A, high molecular polymer PAN is joined in above-mentioned aaerosol solution A the formation mixed liquid B that stirs, the mass ratio of high molecular polymer PAN and aaerosol solution A is 2:30; To be added in cobalt source in above-mentioned mixed liquid B and Keep agitation obtains electrostatic spinning precursor solution C, the mass ratio of cobalt source and mixed liquid B is 0.4:35; Other step is with embodiment 1.
embodiment 7
The purification step of CNTs is: CNTs is placed in container, adds 69wt% red fuming nitric acid (RFNA) under room temperature, and the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:135, magnetic agitation 30min; Then be placed in 120oC oil bath and stir constant temperature 38h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 50oC;
Get the CNTs after purifying and add sonic oscillation 2h in the mixed solution of DMF and ethanol, the mass ratio of CNTs and DMF and ethanol is 1:20:8, then 4h is stirred until CNTs evenly spreads in the mixed solution of DMF and ethanol, form aaerosol solution A, high molecular polymer PAN is joined in above-mentioned aaerosol solution A the formation mixed liquid B that stirs, the mass ratio of high molecular polymer PAN and aaerosol solution A is 2:40; To be added by cobaltous sulfate in above-mentioned mixed liquid B and Keep agitation obtains electrostatic spinning precursor solution C, the mass ratio of cobalt source and mixed liquid B is 0.4:45; Other step is with embodiment 1.
embodiment 8
The purification step of CNTs is: CNTs is placed in container, adds 69wt% red fuming nitric acid (RFNA) under room temperature, and the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:140, magnetic agitation 20min; Then be placed in 140oC oil bath and stir constant temperature 36h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 60oC; Other step is with embodiment 1.
Cobalt source of the present invention is any one in cobalt chloride, cobalt nitrate, cobaltous sulfate or organic acid cobalt salt.Described organic solvent is DMF, ethanol or both mixed solutions.Above about specific descriptions of the present invention, be only not limited to the technical scheme described by the embodiment of the present invention for illustration of the present invention.Those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement, to reach identical technique effect.Needs are used, all in protection scope of the present invention as long as meet.
Claims (9)
- The preparation method of 1.PAN/CoCl2/CNTs composite nano fiber, is characterized in that comprising the steps:Step 1, get the CNTs after purifying and add organic solvent for ultrasonic vibration 1-3h, the mass ratio of CNTs and organic solvent is 0.05-1:28, then 2-4h is stirred until CNTs evenly spreads in organic solvent, form aaerosol solution A, high molecular polymer PAN is joined in above-mentioned aaerosol solution A the formation mixed liquid B that stirs, the mass ratio of high molecular polymer PAN and aaerosol solution A is 2:20-40; To be added in cobalt source in above-mentioned mixed liquid B and Keep agitation obtains electrostatic spinning precursor solution C, the mass ratio of cobalt source and mixed liquid B is 0.4:25-45;Step 2, is placed in plastic injector electrostatic spinning by obtained precursor solution C, is connected to by high-voltage anode on the Metallic Nozzle At The Ingot of syringe tip; Negative electrode is connected as receiving terminal with aluminium foil, and at two interpolar high-pressure direct currents; Fixing distance between syringe nozzle and aluminium foil receiver; On aluminium foil, one deck fibrofelt is formed in electrostatic spinning process; Fibrofelt is collected and is placed on drying in vacuum drying oven, obtain target product PAN/CoCl2/CNTs composite nanometer fiber felt.
- 2. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, it is characterized in that in described step 1, the purification step of CNTs is: CNTs is placed in container, 69wt% red fuming nitric acid (RFNA) is added under room temperature, the mass ratio of CNTs and 69wt% red fuming nitric acid (RFNA) is 1:70-200, magnetic agitation 10-30min; Then be placed in 120-160oC oil bath and stir constant temperature 24-48h; Centrifugal, washing repeatedly after reaction terminates, and be placed in vacuum drying chamber in the dry 24h of 50-70oC.
- 3. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, is characterized in that the cobalt source in described step 1 is cobalt chloride, cobalt nitrate, cobaltous sulfate or organic acid cobalt salt.
- 4. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, is characterized in that the organic solvent of described step 1 is DMF, ethanol or both mixed solutions.
- 5. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, it is characterized in that the electrospinning conditions in described step 2 is: voltage is 20kV, distance between syringe nozzle and aluminium foil receiver is 15cm, and syringe flow velocity is 1.0ml/h.
- 6. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, it is characterized in that the aluminium foil receiver adopted in described step 2 is high-speed rotary rotary drum receiver, rotating speed is 500 turns/min.
- 7. the preparation method of PAN/CoCl2/CNTs composite nano fiber according to claim 1, to is characterized in that in described step 2 that fibrofelt is in vacuum drying oven 50 oc vacuumize 12h.
- 8. PAN/CoCl2/CNTs composite nano fiber according to claim 1, is characterized in that at NaBH 4application in hydrogen manufacturing.
- 9. PAN/CoCl2/CNTs composite nano fiber according to claim 8 is at NaBH 4application in hydrogen manufacturing, is characterized in that PAN/CoCl 2/ CNTs composite nano fiber catalyzing N aBH 4the reaction condition of hydrogen manufacturing is 15 oc, 25 oc, 35 oc or 45 oc; Reuse 5 times.
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Cited By (7)
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| CN107321383A (en) * | 2017-06-20 | 2017-11-07 | 桂林电子科技大学 | A kind of nano-fibre supported cobalt silver alloy and its preparation method and application |
| CN108166091A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of porous composite nano fiber and its preparation and electrode |
| CN109056193A (en) * | 2018-07-04 | 2018-12-21 | 东华大学 | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film |
| CN110280247A (en) * | 2019-07-11 | 2019-09-27 | 辽宁石油化工大学 | A kind of carbon fibre material load C oB method for preparing catalyst and its purposes in terms of preparing hydrogen by sodium borohydride hydrolysis |
| CN113502557A (en) * | 2021-06-28 | 2021-10-15 | 深圳职业技术学院 | Antibacterial modified polyacrylate fiber and preparation method and application thereof |
| CN113991130A (en) * | 2021-10-27 | 2022-01-28 | 西安热工研究院有限公司 | Polyacrylonitrile fiber loaded cobalt-nickel alloy composite oxygen reduction catalytic material and preparation method thereof |
| CN114308040A (en) * | 2022-01-07 | 2022-04-12 | 桂林电子科技大学 | CoB-LDH-CNT (cobalt-layered double hydroxide) -CNT (carbon nanotube) nanomaterial with lamellar structure as well as preparation method and application thereof |
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| CN108166091A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of porous composite nano fiber and its preparation and electrode |
| CN107321383A (en) * | 2017-06-20 | 2017-11-07 | 桂林电子科技大学 | A kind of nano-fibre supported cobalt silver alloy and its preparation method and application |
| CN107321383B (en) * | 2017-06-20 | 2020-08-28 | 桂林电子科技大学 | Nano-fiber-loaded cobalt-silver alloy material and preparation method and application thereof |
| CN109056193A (en) * | 2018-07-04 | 2018-12-21 | 东华大学 | The preparation method and application of flexible sulphur/polyacrylonitrile/carbon nano tube composite fibre film |
| CN110280247A (en) * | 2019-07-11 | 2019-09-27 | 辽宁石油化工大学 | A kind of carbon fibre material load C oB method for preparing catalyst and its purposes in terms of preparing hydrogen by sodium borohydride hydrolysis |
| CN113502557A (en) * | 2021-06-28 | 2021-10-15 | 深圳职业技术学院 | Antibacterial modified polyacrylate fiber and preparation method and application thereof |
| CN113991130A (en) * | 2021-10-27 | 2022-01-28 | 西安热工研究院有限公司 | Polyacrylonitrile fiber loaded cobalt-nickel alloy composite oxygen reduction catalytic material and preparation method thereof |
| CN113991130B (en) * | 2021-10-27 | 2024-01-19 | 西安热工研究院有限公司 | Polyacrylonitrile fiber supported cobalt-nickel alloy composite oxygen reduction catalytic material and preparation method thereof |
| CN114308040A (en) * | 2022-01-07 | 2022-04-12 | 桂林电子科技大学 | CoB-LDH-CNT (cobalt-layered double hydroxide) -CNT (carbon nanotube) nanomaterial with lamellar structure as well as preparation method and application thereof |
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