CN107482231A - A kind of spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer and preparation method thereof - Google Patents
A kind of spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer and preparation method thereof Download PDFInfo
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- CN107482231A CN107482231A CN201710645397.3A CN201710645397A CN107482231A CN 107482231 A CN107482231 A CN 107482231A CN 201710645397 A CN201710645397 A CN 201710645397A CN 107482231 A CN107482231 A CN 107482231A
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
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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
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Abstract
The present invention discloses spherical Pt/ charings stalk compound material of a kind of fine and close three-dimensional manometer and preparation method thereof, fresh stalk is handled using the method for high temperature carbonization, electric conductivity is made it have, the stalk surface for then loading to simple substance Pt after charing using cyclic voltammetry.Three-dimensional Pt nano-particles prepared by the inventive method have nanometer chondritic, the structure is completely encapsulated in charing stalk surface, increase the specific surface area of charing stalk, considerably increase the electro-chemical activity of the composite, be also beneficial to absorption of the methanol on its surface.The present invention is to carbonize stalk as the substrate of composite, its wide material sources, cheap and have reproducibility, meets economic and environment-friendly, green production requirement.And its preparation method is easy, concise in technology, has stronger Modulatory character, thus there is economic feasibility.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to a kind of fine and close spherical Pt/ charings stalk of three-dimensional manometer is compound
Material and preparation method thereof.
Background technology
The energy is that the mankind depend on for existence and the important substance of social development basis, is the lifeblood of the national economic development.In recent years
Come, due to fossil fuel resource shortage and its environmental pollution caused by is on the rise, and causes unusual weather conditions.Therefore, generation
Research of the various countries of boundary to new energy is increasingly paid attention to.Fuel cell is that chemical energy is converted into by one kind by electrochemical reaction
The TRT of electric energy, it has efficient, environmentally friendly, noise low and high reliability, thus by countries in the world
The great attention of government, enterprise and related research institutes.Since early 1960s come out, just develop rapidly as the world
One of focus in new and high technology competition.As future source of energy storage and the ideal chose of conversion equipment, direct methanol fuel electricity
Pond (DMFC) have the advantages that fuel easily transport and storage, in light weight, small volume, simple in construction, energy efficiency it is high and increasingly by
To extensive concern.
One kind that DMFC belongs in Proton Exchange Membrane Fuel Cells (PEMFC), directly using methanol-water
Solution or steam methane are that fuel supplies source, without the reformation hydrogen production by methanol, gasoline and natural gas for generating.But
Because its catalyst is less efficient, catalysis is with high costs, and DMFC is not carried out being commercialized so far.Cause
This, reduces its catalyst cost, structure efficient stable, especially cheap Catalytic Layer, anode catalyst layer, it has also become at present
The outstanding problem faced.Noble metal platinum (Pt) has very high electro catalytic activity to methanol, and it is also to be used as methanol etc. at first to have
The catalyst of machine small molecule electrocatalysis oxidation reaction, it is considered to be preferable anode catalysts for direct methanol fuel cell material.
But its catalytic stability is poor, and high cost also limit its commercial applications.Therefore, developing low-cost, it is high-performance, steady
Qualitative good catalyst material is one of focus of current DMFC technical research.
The content of the invention
The object of the present invention is to solve in the prior art the problems such as catalyst activity is low, stability is poor, cost is high, there is provided
A kind of spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer and preparation method thereof, obtained Pt/ charing stalk is compound
Material has excellent stability and electro-chemical activity, and raw material is easy to get, and technique is simple, economic green, easily realizes industry
Change.
The technical solution adopted in the present invention is：A kind of system of the spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer
Preparation Method, comprise the following steps：(1), straw under high temperature is handled, obtains carbonizing stalk；(2), using three-electrode system, electricity is passed through
Pt is supported on charing stalk surface by the method for deposition, obtains Pt/ charing stalks.
Step (1) the high temperature treatment conditions are, under the protection of nitrogen, by stalk with 1~5 DEG C/min speed liter
Temperature is up to 850 DEG C and is incubated 1~5h, is cooled to room temperature taking-up.Preferably, nitrogen protection be in nitrogen atmosphere, with 3~
10m3/ h 10~60min of flow maintaining nitrogen purge is with displaced air.The high-temperature process is preferably carried out in atmosphere tube type stove.
Preferable, the stalk in step (1) washs drying in advance, after specific method is is ultrasonically treated by ionized water,
Ion water washing is used again, is then dried.
Three-electrode system in the step (2), it is the platinum electrode conduct pair using saturated calomel electrode as reference electrode
Electrode, charing stalk is as working electrode.
Electro-deposition method in the step (2) is cyclic voltammetry.Wherein, electrolyte is sulfuric acid (H2SO4), formic acid
Or acetic acid (CH (HCOOH)3COOH any and chloroplatinic acid (H in)2PtCl6) mixed solution；H in electrolyte2SO4, HCOOH or
CH3COOH concentration and H2PtCl6Concentration ratio be (0.001~1):(0.001~1), it is preferable that the H2SO4, HCOOH or
CH3COOH concentration is 0.001~1mol/L, the H2PtCl6Concentration be 0.001~0.5mol/L；It is further preferably described
H2SO4, HCOOH or CH3COOH concentration is 0.5mol/L, H2PtCl6Concentration be 0.005mol/L.Preferably, electro-deposition is joined
Number is：Scanning low-voltage is -0.4V, and scanning high voltage is 1.4V, scans the number of turns：20~200 circles.
Present invention also offers the Pt/ being prepared by the above method to carbonize stalk compound material.Resulting materials have
Fine and close three-dimensional manometer chondritic.
Compared with prior art, the present invention has positive effect：
(1) the Pt/ charing stalk compound materials that prepared by the present invention, spherical Pt nano-particles uniform close are supported on charing
Stalk surface, this structure considerably increase the specific surface area of prepared Pt/ charing stalk compound materials, its electro-chemical activity
Area substantially increases.
(2) three-dimensional globular structure Pt/ of the invention charing stalk compound material has higher conductance, its electron transmission
Speed is fast, high sensitivity, stability are good.
(3) three-dimensional globular structure Pt/ of the invention charing stalk compound material, preparation technology is simple, and raw material stalk is easy to get
And it is cheap, secondary pollution is not produced, green economy environmental protection, is easy to implement industrialized production.
Brief description of the drawings
Fig. 1 is the SEM spectrum that Pt/ prepared by the embodiment of the present invention 1 carbonizes stalk.
Fig. 2 is the XRD diffracting spectrums that Pt/ prepared by the embodiment of the present invention 1 carbonizes stalk.
Fig. 3 is the circulation that Pt/ charing stalks prepared by the embodiment of the present invention 1 are determination of electrode sulfuric acid and methanol mixed solution
Volt-ampere collection of illustrative plates.
Embodiment
Further detailed description is done to the present invention below in conjunction with the drawings and specific embodiments.The following example is only
The exemplarily description and interpretation present invention, and it is not necessarily to be construed as limiting the scope of the invention.It is all to be based in the present invention
State in the range of the technology that content is realized is encompassed by it is contemplated that protecting.
In order that data have it is certain comparative, identical electro-deposition parameter and at a temperature of to different acid mediums
Pt load is carried out for electrolyte.The charing stalk after Pt is plated to survey using cyclic voltammetry in the mixed solution of sulfuric acid/methanol
Try its electro catalytic activity to methanol.Test condition is unified for：
Electrolyte：0.5mol/L H2SO4With 0.5mol/L CH3OH mixed solution；
Potential scanning speed=10mV/s；
Electrolyte temperature：25℃.
(embodiment 1)
Rear stalk will be dried and take the more regular part of shape, first used again after terminating with deionized water ultrasound 20min, ultrasound
Deionized water is washed, and is finally putting into baking oven and is dried.In the atmosphere of nitrogen, the stalk of cleaning is placed in diamond spar boat, with
3m3/ h flow continues to lead into atmosphere tube type stove nitrogen 30min with displaced air.With 1 DEG C/min speed heating until 850
DEG C and be incubated 3h, be cooled to room temperature taking-up.
Using three-electrode system, reference electrode is saturated calomel electrode, is platinum electrode to electrode, and working electrode is charing
Stalk afterwards, electrolyte are 0.5mol/L H2SO4With 0.005mol/L H2PtCl6Mixed solution.Entered using cyclic voltammetry
Row Pt load, obtain Pt/ charing stalk materials.Wherein cyclic voltammetric parameter is：Low voltage range -0.4V is scanned, scanning is high
Voltage range 1.4V, scan period are 100 times.
Such as Fig. 1, the SEM spectrum of gained Pt/ charing stalks shows that spherical Pt nano-particles uniform close is supported on charing
Stalk surface；
Such as Fig. 2, the XRD diffracting spectrums of Pt/ charing stalks are shown, in the XRD of the Pt/ charing stalks of the present embodiment synthesis
2 θ have corresponding diffraction maximum at 25.9 °, 39.7 °, 46.4 °, 67.5 ° and 81.2 °, wherein 25.9 ° of (002) for corresponding to C
Crystal face；39.7 °, 46.4 °, 67.5 ° and 81.2 ° (111) for corresponding respectively to Pt, (200), (220) and (311) crystal face；
Such as Fig. 3, stalk is carbonized using Pt/ and uses cyclic voltammetry survey in the mixed solution of sulfuric acid/methanol as working electrode
The cyclic voltammetric collection of illustrative plates for trying its electro catalytic activity to methanol shows that the Pt/ of the present embodiment synthesis carbonizes the oxidation of stalk electrode
It is respectively 850mV and 560mV to reduce spike potential, and spike potential difference is 290mV.Find out from its cyclic voltammetric collection of illustrative plates, go out at 850mV
An especially acute oxidation peak is showed, oxidation peak current value also has and significantly increased very much, and this shows electron transport rate
Increase improves its sensitivity, and electro-chemical activity significantly increases.
(embodiment 2)
Method pretreated straw in reference implementation example 1, in the atmosphere of nitrogen, the stalk of cleaning is placed in diamond spar boat
In, with 10m3/ h flow continues to lead into atmosphere tube type stove nitrogen 10min with displaced air, is heated up with 3 DEG C/min speed
Up to 850 DEG C and 5h is incubated, is cooled to room temperature taking-up.
Using three-electrode system, reference electrode is saturated calomel electrode, is platinum electrode to electrode, and working electrode is charing
Stalk afterwards.With 0.5mol/L HCOOH and 0.005mol/L H2PtCl6Mixed solution be electrolyte, using cyclic voltammetry
Pt loads are carried out, obtain Pt/ charing stalk materials.Wherein cyclic voltammetric parameter is：Low voltage range -0.4V is scanned, is swept
High voltage range 1.4V is retouched, the scan period is 50 times.
(embodiment 3)
After method pretreated straw in reference implementation example 1, in the atmosphere of nitrogen, the stalk of cleaning is placed in diamond spar boat
In, with 5m3/ h flow continues to lead into atmosphere tube type stove nitrogen 20min with displaced air, with 5 DEG C/min speed heating direct
To 850 DEG C and 1h is incubated, is cooled to room temperature taking-up.
Using three-electrode system, reference electrode is saturated calomel electrode, is platinum electrode to electrode, and working electrode is charing
Stalk afterwards.With 0.5mol/L CH3COOH and 0.005mol/L H2PtCl6Mixed solution be electrolyte, using cyclic voltammetric
Method carries out Pt loads, obtains Pt/ charing stalk materials.Wherein cyclic voltammetric parameter is：Low voltage range -0.4V is scanned,
High voltage range 1.4V is scanned, the scan period is 200 times.
It should be appreciated that specific embodiment described above is only used for explaining the present invention, it is not intended to limit the present invention.By
Among the obvious changes or variations that the spirit of the present invention is extended out is still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer, it is characterised in that including following step
Suddenly：(1), straw under high temperature is handled, obtains carbonizing stalk；(2), using three-electrode system, Pt is born by the method for electro-deposition
Charing stalk surface is loaded in, obtains Pt/ charing stalks.
2. preparation method according to claim 1, it is characterised in that step (1) the high temperature treatment conditions are, in nitrogen
Under the protection of gas, stalk up to 850 DEG C and is incubated 1~5h with 1~5 DEG C/min speed heating, is cooled to room temperature taking-up.
3. preparation method according to claim 2, it is characterised in that nitrogen protection be in nitrogen atmosphere, with 3~
10m3/ h 10~60min of flow maintaining nitrogen purge is with displaced air.
4. preparation method according to claim 1, it is characterised in that the three-electrode system in the step (2), be with full
With calomel electrode as reference electrode, platinum electrode is used as to electrode, and charing stalk is as working electrode.
5. preparation method according to claim 1, it is characterised in that the electro-deposition method in the step (2) is circulation
Voltammetry；Wherein, electrolyte H2SO4, HCOOH or CH3Any and H in COOH2PtCl6Mixed solution.
6. preparation method according to claim 5, it is characterised in that H in the electrolyte2SO4, HCOOH or CH3COOH
Concentration be 0.001~1mol/L, the H2PtCl6Concentration be 0.001~0.5mol/L, H in electrolyte2SO4, HCOOH or
CH3COOH concentration and H2PtCl6Concentration ratio be (0.001~1):(0.001~1).
7. preparation method according to claim 6, it is characterised in that the electro-deposition parameter in the step (2) is：Scanning
Low-voltage is -0.4V, and scanning high voltage is 1.4V, scans the number of turns：20~200 circles.
8. preparation method according to claim 1, it is characterised in that the stalk in step (1) washs drying in advance, specifically
Then method is dried for after being ultrasonically treated by ionized water, then with ion water washing.
9. according to any described preparation methods of claim 1-8, it is characterised in that prepared Pt/ charing stalks, which have, to be caused
Close three-dimensional manometer chondritic.
What 10. a kind of preparation method according to any of the above-described was prepared has the spherical Pt/ charings of fine and close three-dimensional manometer
Stalk compound material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785980A (en) * | 2020-06-16 | 2020-10-16 | 华东理工大学 | Biomass-based catalyst for direct formic acid fuel cell anode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
| CN103691429A (en) * | 2014-01-03 | 2014-04-02 | 北京林业大学 | Catalyst for rapid pyrolysis and liquefaction of biomass as well as preparation method and application thereof |
| CN104451782A (en) * | 2014-12-01 | 2015-03-25 | 上海师范大学 | Octahedral platinum nanoparticles as well as synthesis method and application thereof |
| CN105431230A (en) * | 2013-08-01 | 2016-03-23 | 南洋理工大学 | Method for forming noble metal nanoparticles on a support |
-
2017
- 2017-08-01 CN CN201710645397.3A patent/CN107482231A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
| CN105431230A (en) * | 2013-08-01 | 2016-03-23 | 南洋理工大学 | Method for forming noble metal nanoparticles on a support |
| CN103691429A (en) * | 2014-01-03 | 2014-04-02 | 北京林业大学 | Catalyst for rapid pyrolysis and liquefaction of biomass as well as preparation method and application thereof |
| CN104451782A (en) * | 2014-12-01 | 2015-03-25 | 上海师范大学 | Octahedral platinum nanoparticles as well as synthesis method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄凯鲁: "负载型铂基纳米电极的制备及电催化性能研究", 《中国优秀硕士学位论文全文数据库-工程科技Ⅱ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785980A (en) * | 2020-06-16 | 2020-10-16 | 华东理工大学 | Biomass-based catalyst for direct formic acid fuel cell anode and preparation method thereof |
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Application publication date: 20171215 |