CN107742733A - A kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon - Google Patents
A kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon Download PDFInfo
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- CN107742733A CN107742733A CN201711018982.7A CN201711018982A CN107742733A CN 107742733 A CN107742733 A CN 107742733A CN 201711018982 A CN201711018982 A CN 201711018982A CN 107742733 A CN107742733 A CN 107742733A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- Y02E60/50—Fuel cells
Abstract
The present invention provides a kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon.This method is first using coal as carbon source, through pre-oxidation treatment, oxidized coal is made, oxidized coal and polyacrylonitrile are configured to certain density spinning solution, using method of electrostatic spinning, control voltage, spinning solution inject speed, receive the parameters such as distance, prepare carbon fiber precursor, then charing process is carried out, prepares the coal-based carbon fiber of size uniform；Again using the coal-based carbon fiber of preparation as carrier, using palladium bichloride as palladium source, ethylene glycol be reducing agent under conditions of prepare the fiber-loaded palladium catalyst of coal-based carbon.The obtained fiber-loaded palladium catalyst of coal-based carbon has good Oxidation of Formic Acid electrocatalysis characteristic.The present invention high-performance carbon fibre composite of preparation, not only has potential application prospect using the coal resources of rich reserves as carbon source in terms of fuel cell, and realizes the high value added utilization of coal, thus has important practical significance.
Description
Technical field
The present invention relates to a kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon.
Background technology
With great attention of the countries in the world to energy crisis and problem of environmental pollution, develop new and effective clean energy resource into
For one of focus of international research and exploitation.Fuel cell is efficient, cleaning energy source device universally acknowledged at present, is had all
More advantages, such as efficient, environment friendly and pollution-free, fuel source conveniently, are referred to as the green energy resource of 21 century.In recent years to formic acid
The research for making the direct methanoic acid fuel cell (DFAFC) of fuel instead of methanol attracts tremendous attention.DFAFC has lot of advantages, such as first
Acid is nontoxic, nonflammable, storage and transportation safety are convenient.Although DFAFC has many advantages, such as, its conventional precious metals pd base
Catalyst still has the shortcomings of expensive, Oxidation of Formic Acid electro-catalysis less stable, therefore how to reduce Pd dosage, carries
High Pd catalytic efficiency, the Pd base catalyst stablized are the problem of one of DFAFC development are extremely important.
The selection of catalyst carrier has a major impact for its catalytic activity, on the one hand carrier can increase load nano particle
Decentralization, improve electrocatalytic reaction needed for electrochemical surface area so that catalyst possesses good activity, the opposing party
The growth process of the nano-particle of load is slowed down in face, so as to improve the stability of catalyst.Preferable electro-catalyst carrier is necessary
It is provided simultaneously with the conditions such as high-specific surface area, high conductivity, suitable pore structure, corrosion-resistant and suitable surface group.Carbon is fine
Dimension is a kind of porous fiber shape material being prepared through high temperature carbonization, activation, with draw ratio is big, specific surface area is high, leads
Electric rate is high, chemical stability is high, has the advantages that abundant micropore.Its huge specific surface area, urged to improve carried noble metal
The dispersiveness of agent and the dosage of reduction noble metal catalyst provide advantage；The performance of high conductivity, it is transmission electrode
Electronics caused by reaction is provided convenience approach；High chemical stability, to prevent the corrosion of electrolyte in battery from providing effectively
Ensure；Abundant microcellular structure, advantage is provided to improve the stability of membrane electrode catalytic layer 3-D solid structure.These
Characteristic enables superior catalytic agent carrier of the carbon fiber as fuel cell.
Coal has rich reserves, phosphorus content height, rich in the characteristic such as aromatic hydrocarbons and hetero atom, can be used as it excellent
Fuel and industrial chemicals, it is alternatively arranged as obtaining the raw material of high added value carbon material.If Functional carbon is prepared from molecular level
Material and its composite, it is expected to develop into coal resources cleaning, efficient and high value added utilization new way.Therefore by coal
Coal-based carbon fibrous material is prepared as carbon source, and as the carrier of Pd base catalyst, it is fine to research and develop new coal-based carbon
Dimension loaded palladium catalyst will have important practical significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon.
The present invention relates to a kind of catalytic composite material of the fiber-loaded palladium of coal-based carbon, its composition is palladium/coal-based carbon fiber,
Synthesis step includes the following steps.
(1) 10g coal dusts are placed in ice-water bath, stir the 240 mL concentrated sulfuric acids of lower addition:Concentrated nitric acid=1:1 (volume ratio) is mixed
Liquid is closed, stands to add after 48h after the dilution of 3L water and filters, washing, dries, obtains oxidized coal.
(2) 0.8g polyacrylonitrile is dissolved in 10mL DMFs at 70 DEG C, adds 0.8g oxidation
Coal, mix overnight, spinning solution is made.
(3) spinning solution is added in syringe, on the syringe pump of electrostatic spinning machine, in the kV of voltage 20, spun
Silk liquid carries out spinning under conditions of injecting speed 0.9mL/h, reception distance 20cm, obtains precursor fibre non-woven fabrics.
(4) obtained precursor fibre non-woven fabrics is fixed on porcelain boat, with 1 °C/min heating speed in Muffle furnace
Rate rises to 280 DEG C, and 3 h of insulation are pre-oxidized, then the fiber of pre-oxidation is arranged in temperature programmed control high temperature process furnances, in N2
In atmosphere, 800 DEG C are risen to 5 DEG C/min heating rate, it is naturally cooling to room temperature after being incubated 3h, it is fine that coal-based carbon is made
Dimension.
(5) 0.04 g coal-based carbons fibers add 20 mL ethylene glycol and 5mL isopropanols, the min of ultrasonic disperse 30, add 20
ML palladium bichlorides containing 0.0167g ethylene glycol solution and 0.03 mL concentrated hydrochloric acids, after stirring, add the mol L of 0.9 mL 4-1
The KOH aqueous solution, more than the h of magnetic agitation 3, is sufficiently mixed it.
(6) mixture in step (5) under the conditions of 160 DEG C of normal pressure is heated to reflux that 12 h are stirred at room temperature after 3 h.
(7) product obtained in step (6) is fully washed with the high purity water of big calorimetric, 60 DEG C of 12 h of vacuum drying.
Brief description of the drawings
Fig. 1 is of the invention using coal as carbon source, the stereoscan photograph of the coal-based carbon fiber prepared using method of electrostatic spinning, by
Photo can be seen that, the coal-based carbon Fiber Aspect Ratio of preparation is big, size uniform.
Fig. 2 is stereoscan photograph of the present invention using coal-based carbon fiber as carrier loaded palladium catalyst material, can by photo
Find out, Pd nano particle has been loaded on coal-based carbon fiber, and particle diameter is about several nanometers.
Fig. 3 is the CV curves of the Oxidation of Formic Acid electro-catalysis of the fiber-loaded palladium catalyst of coal-based carbon prepared by the present invention, by scheming
It can be seen that, the peak that spike potential is 0.14V is Oxidation of Formic Acid peak, and current density is 450mA mg-1 Pd, it is good to illustrate that the catalyst has
Good formic acid electrocatalysis characteristic.
Embodiment
Embodiment 1
10g coal dusts are placed in ice-water bath, stir the 240 mL concentrated sulfuric acids of lower addition:Concentrated nitric acid=1:The mixed liquor of 1 (volume ratio),
Added after standing 48h after 3L water dilutes and filter, wash, be dry, obtain oxidized coal；0.8g oxidized coals are added at 70 DEG C again and dissolved
The 10mL DMFs of 0.8g polyacrylonitrile, mix overnight, then add it in syringe, in electrostatic
On the syringe pump of spinning-drawing machine, spun under conditions of the kV of voltage 20, spinning solution inject speed 0.9mL/h, receive distance 20cm
Silk, obtains precursor fibre non-woven fabrics；Presoma is risen to 280 DEG C with 1 DEG C/min heating rate again, 3 h of insulation carry out pre-
Oxidation, the fiber after pre-oxidation is arranged in temperature programmed control high temperature process furnances, in N2In atmosphere, with 5 DEG C/min heating rate
800 DEG C are risen to, it is naturally cooling to room temperature after being incubated 3h, coal-based carbon fiber is made.In coal-based carbon fiber made from 0.04 g
20 mL ethylene glycol of middle addition and 5mL isopropanols, the min of ultrasonic disperse 30, then add the second of 20 mL palladium bichlorides containing 0.0167g
Glycol solution and 0.03 mL concentrated hydrochloric acids, after stirring, add the mol L of 0.9 mL 4-1The KOH aqueous solution, the h of magnetic agitation 3
More than, it is heated to reflux that 12 h are stirred at room temperature after 3 h under the conditions of 160 DEG C of normal pressure, is fully washed with the high purity water of big calorimetric, 60 DEG C
12 h are dried in vacuo, produce the fiber-loaded palladium catalyst material of coal-based carbon.
Claims (2)
1. a kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon, it is characterised in that follow these steps to carry out：By 10g coal dusts
It is placed in ice-water bath, stirs the 240 mL concentrated sulfuric acids of lower addition:Concentrated nitric acid=1:The mixed liquor of 1 (volume ratio), added after standing 48h
Filter, wash, dry after the dilution of 3L water, obtain oxidized coal；0.8g polyacrylonitrile is dissolved in 10mL N, N- dimethyl at 70 DEG C
Formamide, then 0.8g oxidized coals are added in the solution, mix overnight, spinning solution is made；Spinning solution is added to injection
In device, on the syringe pump of electrostatic spinning machine, speed 0.9mL/h, reception distance are injected in the kV of voltage 20, spinning solution
Spinning is carried out under conditions of 20cm, obtains precursor fibre non-woven fabrics；Obtained precursor fibre non-woven fabrics is fixed on porcelain again
On boat, 280 DEG C are risen to 1 DEG C/min heating rate in Muffle furnace, 3 h of insulation are pre-oxidized, then the fibre by pre-oxidation
Dimension is arranged in temperature programmed control high temperature process furnances, in N2In atmosphere, 800 DEG C are risen to 5 DEG C/min heating rate, after being incubated 3h
It is naturally cooling to room temperature, coal-based carbon fiber is made；20 mL ethylene glycol and 5mL isopropyls are added in 0.04 g coal-based carbon fibers
Alcohol, the min of ultrasonic disperse 30, the ethylene glycol solution and 0.03 mL concentrated hydrochloric acids of 20 mL palladium bichlorides containing 0.0167g are then added, is stirred
After mixing uniformly, the mol L of 0.9 mL 4 are added-1The KOH aqueous solution, more than the h of magnetic agitation 3, is sufficiently mixed it, 160 DEG C of normal pressure
Under the conditions of be heated to reflux that 12 h are stirred at room temperature after 3 h, filter fully washing, 60 DEG C of vacuum drying 12 with big calorimetric high purity water
H, the fiber-loaded palladium catalyst of coal-based carbon is made.
2. preparation method according to claim 1, the fiber-loaded palladium catalyst of coal-based carbon of gained has to Oxidation of Formic Acid
Good electro catalytic activity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110926663A (en) * | 2019-12-03 | 2020-03-27 | 东华大学 | Preparation method of washable wearable high-sensitivity pressure sensor |
| CN110943232A (en) * | 2019-12-26 | 2020-03-31 | 辽宁科技大学 | Preparation method of metal air battery electrocatalyst based on coal self-growing carbon nano tube |
| CN113713765A (en) * | 2021-08-30 | 2021-11-30 | 大连海事大学 | Preparation method and application of coal-based hollow fiber carbon membrane |
| CN114267829A (en) * | 2021-12-08 | 2022-04-01 | 新疆大学 | Preparation method of coal-based porous carbon fiber negative electrode material of lithium/sodium ion battery |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546759A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method for preparing nanometer carbon fiber by coal |
| CN101279255A (en) * | 2008-04-17 | 2008-10-08 | 中国科学院上海微系统与信息技术研究所 | Method for directly preparing nano-catalyst based on Pd for alcohol fuel battery |
| CN102078811A (en) * | 2010-12-26 | 2011-06-01 | 南京师范大学 | Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method |
| CN103357401A (en) * | 2013-07-03 | 2013-10-23 | 中国科学院长春应用化学研究所 | Preparation method of palladium based catalyst |
| CN103840177A (en) * | 2012-11-27 | 2014-06-04 | 李文鹏 | Formic acid fuel cell anode catalytic material |
| CN103894189A (en) * | 2014-04-23 | 2014-07-02 | 西南大学 | Preparation method of high-performance palladium/graphene methanoic acid oxidation catalyst |
| CN104001510A (en) * | 2014-06-16 | 2014-08-27 | 上海电力学院 | Method for preparing Sb modified Pd film catalyst oriented to formic acid electrooxidation |
| CN105268488A (en) * | 2015-10-23 | 2016-01-27 | 北京中科诚毅科技发展有限公司 | Catalyst support as well as loading method and application thereof |
| CN105401261A (en) * | 2015-12-27 | 2016-03-16 | 常州亚环环保科技有限公司 | Electrolytic oxidization method for preparing coal asphalt based carbon fiber |
| CN105679554A (en) * | 2016-01-05 | 2016-06-15 | 新疆大学 | Preparation method for needle-shaped polyaniline/coal-based carbon nanofiber flexible supercapacitor |
-
2017
- 2017-10-27 CN CN201711018982.7A patent/CN107742733A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546759A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method for preparing nanometer carbon fiber by coal |
| CN101279255A (en) * | 2008-04-17 | 2008-10-08 | 中国科学院上海微系统与信息技术研究所 | Method for directly preparing nano-catalyst based on Pd for alcohol fuel battery |
| CN102078811A (en) * | 2010-12-26 | 2011-06-01 | 南京师范大学 | Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method |
| CN103840177A (en) * | 2012-11-27 | 2014-06-04 | 李文鹏 | Formic acid fuel cell anode catalytic material |
| CN103357401A (en) * | 2013-07-03 | 2013-10-23 | 中国科学院长春应用化学研究所 | Preparation method of palladium based catalyst |
| CN103894189A (en) * | 2014-04-23 | 2014-07-02 | 西南大学 | Preparation method of high-performance palladium/graphene methanoic acid oxidation catalyst |
| CN104001510A (en) * | 2014-06-16 | 2014-08-27 | 上海电力学院 | Method for preparing Sb modified Pd film catalyst oriented to formic acid electrooxidation |
| CN105268488A (en) * | 2015-10-23 | 2016-01-27 | 北京中科诚毅科技发展有限公司 | Catalyst support as well as loading method and application thereof |
| CN105401261A (en) * | 2015-12-27 | 2016-03-16 | 常州亚环环保科技有限公司 | Electrolytic oxidization method for preparing coal asphalt based carbon fiber |
| CN105679554A (en) * | 2016-01-05 | 2016-06-15 | 新疆大学 | Preparation method for needle-shaped polyaniline/coal-based carbon nanofiber flexible supercapacitor |
Non-Patent Citations (1)
| Title |
|---|
| 宋贤丽: ""煤基碳纳米纤维复合材料的制备及其在超级电容器中的应用"", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110926663A (en) * | 2019-12-03 | 2020-03-27 | 东华大学 | Preparation method of washable wearable high-sensitivity pressure sensor |
| CN110943232A (en) * | 2019-12-26 | 2020-03-31 | 辽宁科技大学 | Preparation method of metal air battery electrocatalyst based on coal self-growing carbon nano tube |
| CN110943232B (en) * | 2019-12-26 | 2021-01-05 | 辽宁科技大学 | Preparation method of metal air battery electrocatalyst based on coal self-growing carbon nano tube |
| CN113713765A (en) * | 2021-08-30 | 2021-11-30 | 大连海事大学 | Preparation method and application of coal-based hollow fiber carbon membrane |
| CN114267829A (en) * | 2021-12-08 | 2022-04-01 | 新疆大学 | Preparation method of coal-based porous carbon fiber negative electrode material of lithium/sodium ion battery |
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Application publication date: 20180227 |