CN108963282A - A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction - Google Patents
A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction Download PDFInfo
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- CN108963282A CN108963282A CN201810730256.6A CN201810730256A CN108963282A CN 108963282 A CN108963282 A CN 108963282A CN 201810730256 A CN201810730256 A CN 201810730256A CN 108963282 A CN108963282 A CN 108963282A
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of methods that solvent-thermal method prepares fuel cell carbon carried platinum-based catalyst, are applied in Proton Exchange Membrane Fuel Cells, including hydrogen-air fuel cell and direct alcohol fuel cell cathode reaction, belong to electrochemical catalysis reaction field.The present invention uses solvent-thermal method reduction treatment, carrier carbon material is well dispersed in solvent, metal front liquid solution is added under stiring, the mass percentage of active component reaches 20wt% to 60wt% in catalyst obtained, and then mixed liquor is reacted in the sealed reaction vessel of high temperature and pressure to 9 or more with the pH value of alkaline solution adjusting solution.PH value is adjusted with acid solution after reaction and is lower than 5, and reaction solution is filtered, washed, is dried and obtains carbon-carried platinum-based elctro-catalyst after grinding.Catalyst activity component partial size obtained by the present invention is small, and high uniformity dispersion is on the carbon carrier, activity with higher.Preparation process of the invention is easy to operate, rapid reaction, less energy intensive, low in cost, it is easy to accomplish large-scale industrial production.
Description
Technical field
The invention belongs to catalyst of fuel batter with proton exchange film field, including hydrogen-air fuel cell catalyst and directly
Alcohol fuel cell catalyst is related to a kind of preparation method of carbon-carried platinum-based material, more particularly to is existed using sealed reaction vessel
Solvothermal preparation method and application under high temperature and pressure.
Background technique
Fuel cell is a kind of energy conversion device for converting chemical energy to electric energy, has energy conversion efficiency height, ring
Border pollution is small and fuel carries the advantages that supplement facilitates and pays close attention to by people.Proton Exchange Membrane Fuel Cells (PEMFC), due to
Has many advantages, such as energy density height, low operation temperature, pollution-free and receive much attention.There are two types of the fuel source of PEMFC is general: one
Kind is directly known as hydrogen-air fuel cell as fuel using pure hydrogen or reformation hydrogen rich gas；Another kind is directly to utilize organic small point
Son is known as direct fuel cell as fuel, such as is directly known as direct Aalcohols fuel electricity using the battery that methanol (ethyl alcohol) does fuel
Pond (DAFC).Hydrogen-oxygen fuel cell using hydrogen as unstripped gas is optimal electrochmical power source, the electrification that it occurs when working
Learning reaction product is clean water, does not have any pollution to environment.And direct methanol fuel cell is because it is with solid-state polymerization substance
Proton exchange is electrolyte, is directly fuel using liquid methanol, reforms without external, ground extensively in past 20 years
Study carefully, and is believed to the power supply that development is portable electronic device and electric vehicle.
However, Cathodic oxygen reduction (ORR) is the bottleneck for limiting PEMFC performance, it is slow due to its kinetic rate,
The oxygen reduction reaction catalyst of efficient stable is necessary.All there is at high cost, the service life is short, volatile for catalyst used at present
The disadvantages of living, therefore develop high-activity cathode catalyst and be of great significance for PEMFC commercial applications.
Carbon-carried platinum-based (Pt/C) catalyst is widely used cathod catalyst in current Proton Exchange Membrane Fuel Cells.To the greatest extent
The reserves of precious metals pt needed for pipe catalyst are rare, and price is more expensive, but since its stability in the electrolyte is good, ORR is urged
It is high to change activity, is still considered as best fuel battery cathod catalyst.It is either still opened at present in application in basic research
Hair field, Pt/C catalyst are still the research hotspot of catalyst of fuel batter with proton exchange film.
Currently, the production method of Pt/C has immersion reduction method, pulse microwave to help polyol reduction method, protective agent method, reflux
Method, colloid method and microemulsion method etc., wherein different preparation methods is used, to the active material dispersibility of catalyst, partial size ruler
The physico-chemical properties such as very little, stability have conclusive effect, and the activity of these physico-chemical properties and catalyst is closely related；It is another
Aspect, the cumbersome operating procedure of too complex also can bring obstruction to the large-scale production of catalyst, industrial applications.Such as protection
Agent method can make the nano-noble metal particle of protective agent preparation high degree of dispersion by surfactant or other organic macromolecules, and
It is supported on carrier, even if very high metal dispersion can be obtained by remaining in the higher situation of noble metal loadings
Degree, can prepare the alloy catalyst of multiple element.But this method is to solvent, surfactant or protective agent and operating condition
It is required that very high while complicated for operation, higher cost and it is not easy to produce in enormous quantities.
Summary of the invention
For the deficiency of existing technology of preparing, it is high using sealed reaction vessel high temperature that the purpose of the present invention is to provide a kind of
The method that compacting is ready for use on the carbon-carried platinum-based elctro-catalyst of fuel cell.The present invention can it is simple, effectively, prepare height at low cost
Active carbon-carried platinum-based catalyst, since its reaction is reacted in next step in high-temperature and high-pressure conditions, which easily expands
Metaplasia produces；Meanwhile prepared catalyst granules is small and particle diameter distribution is uniform, catalytic activity is better than existing commercialization pallium-on-carbon
Base.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of carbon-carried platinum-based elctro-catalyst using fuel cell preparation method, method includes the following steps:
1) carbon-based material is passed through ultrasound and stirred evenly and be dispersed in alcoholic solution；Specifically, at room temperature, carbon is carried
Body and alcohols reducing agent are according to the mass ratio mixing of 1:200~900 and fully dispersed；
2) in the solution of step 1) be added dropwise the body containing noble metal precursor solution, and stir it is fully dispersed after mixed liquor；
Noble metal quality in the noble metal precursor body accounts for 20wt%~60wt% of carbon-carried platinum-based elctro-catalyst gross mass, described expensive
Metal precursor is H2PtCl6·6H2O；
3) KOH alcoholic solution or NaOH alcoholic solution, regulating step 2 are used) solution ph that obtains is 9-12, it is fully dispersed
Mixed liquor；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, uses external heat to 110~180
DEG C, obtained reaction solution within heating time 2~5 hours, after reaction solution cooled to room temperature, it is 1- that acid solution is added dropwise dropwise and adjusts pH
4, and be sufficiently stirred；
5) it will be filtered through step 4) treated reaction solution, and wash filter cake with 60 DEG C or more of deionized water, until detecting
In scrub raffinate without chloride ion until, gained filter cake is dried in vacuo, is ground after cooling, obtains solid powder.
The preparation method of carbon-carried platinum-based catalyst of the invention, in step 1), the carbon carrier specifically can be XC-72 carbon
Powder, conductive black, active carbon, carbon nanotube or ordered mesopore carbon etc.；The alcohols reducing agent is ethylene glycol, glycerine or third
Glycol.
The preparation method of carbon-carried platinum-based catalyst of the invention, in step 3), alcoholic solution concentration is 1.0-5.0mol/L,
Alcohol in its alcoholic solution is ethylene glycol, propylene glycol or glycerine.
The preparation method of carbon-carried platinum-based catalyst of the invention, in step 4), the reaction vessel used specifically can be can
Sealed high-voltage resistant container, including stainless steel high pressure sealing reaction vessel, polytetrafluoroethylene (PTFE) high pressure sealing reaction vessel etc.；It uses
Acid-specific can be HNO3Aqueous solution, H2SO4Aqueous solution or HCL aqueous solution；The acid solutions used are 0.1-3.0mol/L,
Mixing time is 3 hours or more.
Catalyst prepared by carbon-carried platinum-based catalyst preparation method of the invention can be applied to pem fuel electricity
In pond, including hydrogen-air fuel cell catalyst and direct alcohol fuel cell.
By above-mentioned technical proposal, the invention has the advantages that and the utility model has the advantages that
1) present invention is reacted under high-temperature and high-pressure conditions using sealed reaction vessel, simply and effectively ensure that reaction
The stability and consistency of environment are not easy to be influenced by the external world and are easy to regulate and control, thus can expand preparative-scale easily, reduce life
Produce cost.
2) due to organic polyhydric alcohol be used as simultaneously dispersing agent and reducing agent, sealed reaction vessel provide stable temperature and
Pressure, a large amount of dispersing methods using stirring and ultrasonic disperse alternately etc., the activity for the carbon-carried platinum-based catalyst prepared
Material grains degree is uniform, tiny, and is uniformly dispersed, not easy to reunite, improves noble metal utilisation, while guaranteeing performance
It reduces costs.
3) catalyst obtained by the present invention is obviously improved compared to existing commercialized catalyst performance.
Detailed description of the invention
Fig. 1 is the Pt/C catalyst transmission electron microscope photo of the 20wt% prepared in the embodiment of the present invention 1.
Fig. 2 is the XRD spectra of the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 1.
Fig. 3 is that the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 1 and 20wt%Pt/C commercial catalysts exist
0.5mol/L H2SO4Linear voltammetric scan figure in solution.
Fig. 4 is the XRD spectra of the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 2.
Fig. 5 is that the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 2 and 20wt%Pt/C commercial catalysts exist
0.5mol/L H2SO4Cyclic voltammetry scan figure in solution.
Fig. 6 is the Pt/C catalyst transmission electron microscope photo of the 40wt% prepared in the embodiment of the present invention 3.
Fig. 7 is the XRD spectra of the Pt/C catalyst of the 60wt% prepared in the embodiment of the present invention 4.
Fig. 8 is the Pt/C catalyst and 60wt%Pt/C commercial catalysts of the 60wt% prepared in the embodiment of the present invention 4
Dynamics current density comparison diagram.
Fig. 9 is the XRD spectra of the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 5.
Figure 10 is that the Pt/C catalyst of the 20wt% prepared in the embodiment of the present invention 5 and 20wt%Pt/C commercial catalysts exist
0.5mol/L H2SO4Linear voltammetric scan figure in solution.
Figure 11 is the Pt/C catalyst and 20wt%Pt/C commercial catalysts of the 20wt% prepared in the embodiment of the present invention 5
Dynamics current density comparison diagram.
Specific embodiment
Elctro-catalyst preparation method of the invention is made below by way of specific preferred embodiment combination attached drawing further detailed
Illustrate, but the present invention is not limited in embodiment below.
The invention discloses a kind of methods that solvent-thermal method prepares fuel cell carbon carried platinum-based catalyst, and in particular to a kind of
The carbon-carried platinum-based catalyst of polyol solvent thermal reduction preparation, is applied to Proton Exchange Membrane Fuel Cells, including hydrogen-oxygen fuel
In battery and direct alcohol fuel cell cathode reaction, belong to electrochemical catalysis reaction field.The present invention uses solvent-thermal method also
Original place reason, carrier carbon material is well dispersed in solvent, and metal front liquid solution, the quality of active component are added under stiring
Percentage composition reaches 20wt% to 60wt% in catalyst obtained, and adjusts the pH value of solution to 9 or more with alkaline solution,
Then mixed liquor is reacted in the sealed reaction vessel of high temperature and pressure.PH value is adjusted to being lower than with acid solution after reaction
5, reaction solution is filtered, washed, is dried and obtains carbon-carried platinum-based elctro-catalyst after grinding.
Catalyst activity component partial size obtained by the present invention is small, and high uniformity dispersion is on the carbon carrier, has higher
Activity.Preparation process of the invention is easy to operate, rapid reaction, less energy intensive, low in cost, it is easy to accomplish high-volume industry
Metaplasia produces.
It is by carbon carrier, solvent, reducing agent, metal salt solution that carbon-carried platinum-based catalyst is directly prepared using solvent-thermal method
Equal raw materials after evenly mixing, are placed in sealed reaction vessel and carry out the easy-to-use method of a step heating.Party's subtraction unit letter
It is single, and easily expand the scale of production, more there are environmentally protective, low power consumption and other advantages.On the other hand, since reaction vessel can mention
For certain temperature and pressure, therefore its carbon-carried platinum-based catalyst active material prepared is uniformly dispersed, partial size is smaller, has
Better fuel cell anode and cathode catalytic activity.
Embodiment 1
A kind of preparation method of the carbon-carried platinum-based catalyst applied to fuel cell, comprises the following steps that:
1) XC-72 that 80mg is bought is weighed with assay balance, and 40.00mL ethylene glycol solution is added, ultrasound and stirring are handed over
For dispersion 1h or more, until XC-72 is evenly dispersed in ethylene glycol solution；
2) 5.25mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) is added dropwise, and is dispersed with stirring 3h or more；
3) be added dropwise 1mol/L NaOH ethylene glycol solution, regulating step 2) obtain solution ph be 11, it is fully dispersed to mix
Close liquid；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, using external heat to 140 DEG C, heating
Obtain reaction solution within 3 hours；After reaction solution cooled to room temperature, 0.5mol/L HNO is added dropwise dropwise3It is 3 that aqueous solution, which adjusts pH,
And it is sufficiently stirred 8 hours；
5) it will be filtered through step 4) treated reaction solution low pressure, and wash filter cake with 60 DEG C or more of deionized water, until
Detect scrub raffinate in without chloride ion until.Gained filter cake is dried in vacuo at 80 DEG C, grinds, obtains carbon-carried platinum-based after cooling
Solid powder.
Transmission electron microscope analysis is carried out with the carbon-carried platinum-based catalyst that the embodiment 1 obtains, as shown in Figure 1, platinum active component
Uniformly, it is distinctly distributed on the carbon carrier.The catalyst dispersity is preferable, less reunion；And partial size is thinner, according to mathematical statistics
Methods analysis chart 1 it can be concluded that, the platinum active component partial size of the catalyst is about 2.0nm, therefore its specific surface area is higher.
XRD diagram spectrum analysis, as seen from Figure 2, the embodiment are carried out with the carbon-carried platinum-based catalyst that the embodiment 1 obtains
The active component platinum of the 20wt%Pt/C catalyst of preparation is face-centred cubic structure, according to Scherrer (Scherrer) formula meter
It calculates, partial size is less than 2.1nm, is consistent substantially with the particle size results of Fig. 1 performance.
Using carbon-carried platinum-based catalyst prepared by the present invention test its oxygen reduction reaction activity, and with commercialization platinum carrying capacity
The carbon-carried platinum-based catalyst of 20wt% tests the active comparison of progress jointly.
For the glass-carbon electrode of the catalyst coating obtained using the embodiment 1 as working electrode, platinum plate electrode is to electrode, saturation
Calomel electrode is reference electrode, using 0.5mol/L H2SO4Linear voltammetric scan test is carried out as electrolyte.As can be seen that
The oxygen reduction activity of the embodiment is much higher than 20wt%Pt/C commercialized catalyst, and the linear voltammetric scan figure of experimentation is attached
Fig. 3, the hydrogen reduction take-off potential of the catalyst of example preparation are 0.95V, half wave potential 0.82V, limiting current density
Up to -4.65mA/cm2, it is superior to 20wt%Pt/C commercialized catalyst.As can be seen that prepared using method of the invention
Catalyst, oxygen reduction activity are obviously improved.
Embodiment 2
A kind of preparation method of the carbon-carried platinum-based catalyst applied to fuel cell, comprises the following steps that:
1) XC-72 that 80mg is bought is weighed with assay balance, and 40.00mL ethylene glycol solution is added, ultrasound and stirring are handed over
For dispersion 1h or more, until XC-72 is evenly dispersed in ethylene glycol solution；
2) 5.25mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) is added dropwise, and is dispersed with stirring 3h or more；
3) be added dropwise 2mol/L KOH ethylene glycol solution, regulating step 2) obtain solution ph be 13, it is fully dispersed to mix
Close liquid；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, using external heat to 140 DEG C, heating
Obtain reaction solution within 2 hours, after reaction solution cooled to room temperature, it is 3 that 0.5mol/L HCL aqueous solution is added dropwise dropwise and adjusts pH, and
It is sufficiently stirred 8 hours；
5) it will be filtered through step 4) treated reaction solution low pressure, and wash filter cake with 60 DEG C or more of deionized water, until
Until detecting in scrub raffinate without chloride ion, gained filter cake is dried in vacuo at 80 DEG C, grinds, obtains carbon-carried platinum-based after cooling
Solid powder.
XRD diagram spectrum analysis, as seen from Figure 4, the embodiment are carried out with the carbon-carried platinum-based catalyst that the embodiment 2 obtains
The active component platinum of the 20wt%Pt/C catalyst of preparation is face-centred cubic structure, according to Scherrer (Scherrer) formula meter
It calculates, partial size is about 3.2nm.
Using carbon-carried platinum-based catalyst prepared by the present invention test its oxygen reduction reaction activity, and with commercialization platinum carrying capacity
The carbon-carried platinum-based catalyst of 20wt% tests the active comparison of progress jointly.
For the glass-carbon electrode of the catalyst coating obtained using the embodiment 2 as working electrode, platinum plate electrode is to electrode, saturation
Calomel electrode is reference electrode, using 0.5mol/L H2SO4Cyclic voltammetry test is carried out as electrolyte, test result is followed
Ring voltammetric scan figure is in attached drawing 5.As can be seen that the hydrogen reduction take-off potential of the catalyst of example preparation is better than 20wt%Pt/C
Commercialized catalyst, oxygen reduction activity are higher than 20wt%Pt/C commercialized catalyst.
Embodiment 3
A kind of preparation method of the carbon-carried platinum-based catalyst applied to fuel cell, comprises the following steps that:
1) XC-72 that 80mg is bought is weighed with assay balance, and 35mL ethylene glycol solution is added, ultrasound and stirring alternately divide
1h or more is dissipated, until XC-72 is evenly dispersed in ethylene glycol solution；
2) 10.5mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) is added dropwise, and is dispersed with stirring 3h or more；
3) be added dropwise 1mol/L NaOH ethylene glycol solution, regulating step 2) obtain solution ph be 13, it is fully dispersed to mix
Close liquid；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, using external heat to 140 DEG C, heating
It obtains reaction solution within 5 hours, after reaction solution cooled to room temperature, 0.5mol/L HNO is added dropwise dropwise3It is 3 that aqueous solution, which adjusts pH,
And it is sufficiently stirred 8 hours；
5) it will be filtered through step 4) treated reaction solution, and wash filter cake with 60 DEG C or more of deionized water, until detecting
In scrub raffinate without chloride ion until, gained filter cake is dried in vacuo at 80 DEG C, is ground after cooling, obtains carbon-carried platinum-based solid
Powder.
Transmission electron microscope analysis is carried out with the carbon-carried platinum-based catalyst that the embodiment 3 obtains, as shown in fig. 6, platinum active component
Uniformly, be distinctly distributed on the carbon carrier, according to mathematical statistics methods analysis chart 6 it can be concluded that, the platinum active group of the catalyst
Gradation diameter is about 3.6nm.The catalyst particle size is thinner, less in the dispersibility that the case where higher platinum carrying capacity has still remain
Reunite.
Embodiment 4
A kind of preparation method of the carbon-carried platinum-based catalyst applied to fuel cell, comprises the following steps that:
1) XC-72 that 80mg is bought is weighed with assay balance, and 40.00mL glycerin solution is added, ultrasound and stirring are handed over
For dispersion 1h or more, until XC-72 is evenly dispersed in glycerin solution；
2) 15.75mL chloroplatinic acid glycerin solution (3.81mg/mL) is added dropwise, and is dispersed with stirring 3h or more；
3) be added dropwise 1mol/L NaOH glycerin solution, regulating step 2) obtain solution ph be 11, it is fully dispersed to mix
Close liquid；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, using external heat to 150 DEG C, heating
It obtains reaction solution within 4 hours, after reaction solution cooled to room temperature, 0.5mol/L HNO is added dropwise dropwise3It is 3 that aqueous solution, which adjusts pH,
And it is sufficiently stirred 8 hours；
5) it will be filtered through step 4) treated reaction solution low pressure, and wash filter cake with 60 DEG C or more of deionized water, until
Until detecting in scrub raffinate without chloride ion, gained filter cake is dried in vacuo at 80 DEG C, grinds, obtains carbon-carried platinum-based after cooling
Solid powder.
XRD diagram spectrum analysis, as seen from Figure 7, the embodiment are carried out with the carbon-carried platinum-based catalyst that the embodiment 4 obtains
The active component platinum of the 60wt%Pt/C catalyst of preparation is face-centred cubic structure, according to Scherrer (Scherrer) formula meter
It calculates, platinum active component partial size is about 5.6nm.
Using carbon-carried platinum-based catalyst prepared by the present invention test its oxygen reduction reaction activity, and with commercialization platinum carrying capacity
The carbon-carried platinum-based catalyst of 60wt% is tested jointly, compares their dynamics current density.
For the glass-carbon electrode of the catalyst coating obtained using the embodiment 4 as working electrode, platinum plate electrode is to electrode, saturation
Calomel electrode is reference electrode, using 0.5mol/L H2SO4Carry out linear voltammetric scan test as electrolyte, and compare its with
With the carbon-carried platinum-based catalyst dynamics current density of commercialization platinum carrying capacity 60wt%.As seen from Figure 8, which prepares
The dynamics current density of catalyst is up to 0.718mA/cm2, electric much higher than the dynamics of 60wt%Pt/C commercialized catalyst
Current density (0.234mA/cm2).This explanation using carbon-carried platinum-based catalyst prepared by the present invention during oxygen reduction reaction by
The degree of diffusing step control is smaller, and mass transport process is carried out rapidly in electrode reaction, is relatively commercialized carbon-carried platinum-based catalysis
For agent, carbon-carried platinum-based catalyst prepared by the present invention has better kinetic reaction rate.
Embodiment 5
A kind of preparation method of the carbon-carried platinum-based catalyst applied to fuel cell, comprises the following steps that:
1) XC-72 that 160mg is bought is weighed with assay balance, and 60.00mL ethylene glycol solution is added, ultrasound and stirring are handed over
For dispersion 1h or more, until XC-72 is evenly dispersed in ethylene glycol solution；
2) 10.50mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) is added dropwise, and is dispersed with stirring 3h or more；
3) be added dropwise 3mol/L NaOH ethylene glycol solution, regulating step 2) obtain solution ph be 11, it is fully dispersed to mix
Close liquid；
4) the resulting mixed liquor of step 3) is placed in high pressure sealing reaction vessel, using external heat to 150 DEG C, heating
It obtains reaction solution within 3 hours, after reaction solution cooled to room temperature, 0.5mol/L H is added dropwise dropwise2SO4It is 2 that aqueous solution, which adjusts pH,
And it is sufficiently stirred 8 hours；
5) it will be filtered through step 4) treated reaction solution, and wash filter cake with 60 DEG C or more of deionized water, until detecting
In scrub raffinate without chloride ion until, gained filter cake is dried in vacuo at 80 DEG C, is ground after cooling, obtains carbon-carried platinum-based solid
Powder.
XRD diagram spectrum analysis, as seen from Figure 9, the embodiment are carried out with the carbon-carried platinum-based catalyst that the embodiment 5 obtains
The active component platinum of the 20wt%Pt/C catalyst of preparation is face-centred cubic structure, according to Scherrer (Scherrer) formula meter
It calculates, platinum active component partial size is about 4.2nm.
Using carbon-carried platinum-based catalyst prepared by the present invention test its oxygen reduction reaction activity, and with commercialization platinum carrying capacity
The carbon-carried platinum-based catalyst of 20wt% tests the active comparison of progress jointly.
For the glass-carbon electrode of the catalyst coating obtained using the embodiment 5 as working electrode, platinum plate electrode is to electrode, saturation
Calomel electrode is reference electrode, using 0.5mol/L H2SO4Linear voltammetric scan test is carried out as electrolyte.As can be seen that
The oxygen reduction activity of the embodiment is much higher than 20wt%Pt/C commercialized catalyst, and the linear voltammetric scan figure of experimentation is attached
Figure 10, hydrogen reduction the take-off potential 0.95V, half wave potential 0.82V of the catalyst of example preparation are superior to 20wt%Pt/C quotient
Industry catalyst.As can be seen that the catalyst prepared using method of the invention, oxygen reduction activity are obviously improved.
The carbon-carried platinum-based catalyst of the catalyst obtained with the embodiment 5 and commercialization platinum carrying capacity 20wt% is tested jointly,
And compare their dynamics current density.As seen from Figure 11, the dynamics electric current of the catalyst of embodiment preparation is close
Degree is up to 0.545mA/cm2, much higher than the dynamics current density (0.094mA/cm of 20wt%Pt/C commercialized catalyst2).This
Illustrate that the degree controlled during oxygen reduction reaction by diffusing step using carbon-carried platinum-based catalyst prepared by the present invention is smaller,
Mass transport process is carried out rapidly in electrode reaction, is relatively commercialized for carbon-carried platinum-based catalyst, and carbon prepared by the present invention carries
Platinum based catalyst has better kinetic reaction rate.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, therefore
Without departing from the technical solutions of the present invention, to the above embodiments according to the technical essence of the invention any simply to repair
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of preparation method of the fuel cell carbon carried platinum-based catalyst of solvent-thermal method reduction, which is characterized in that this method packet
Include following steps:
1) at room temperature, carbon carrier and alcohols reducing agent are mixed and fully dispersed according to the mass ratio of 1:200~900；
2) solution of the body containing noble metal precursor is added dropwise in the mixed liquor of step 1), and mixed liquor is sufficiently stirred to obtain；
3) it is added in the mixed solution that KOH alcoholic solution or NaOH alcoholic solution are obtained to step 2), adjusting pH value is 8-14, is sufficiently stirred
It mixes, the pre-reaction mixed liquor handled well can be obtained；
4) the resulting mixed liquor of step 3) is placed in sealed reaction vessel, control reaction temperature is 120 DEG C~200 DEG C, heating 1
Reaction solution is obtained after~6 hours, after reaction solution is cooled to room temperature, it is 1~4 that acid solution is added dropwise under stiring and adjusts pH, stirring 2
~12 hours；
5) the resulting reaction solution of step 4) is filtered, and filter cake is washed with deionized, until without chloride ion in detection scrub raffinate
Until, it will be ground after gained filtration cakes torrefaction, obtain solid powder.
2. according to the method described in claim 1, it is characterized by: the carbon carrier is XC-72 carbon dust, conduction in step 1)
Carbon black, active carbon, carbon nanotube or ordered mesopore carbon etc.；The alcohols reducing agent is ethylene glycol, glycerine or propylene glycol.
3. according to the method described in claim 1, it is characterized by: the noble metal precursor body is chloroplatinic acid in step 2)
(H2PtCl6·6H2O) etc.；The carbon carrier after body containing noble metal precursor is added dropwise needs that dispersion is sufficiently stirred, and mixing time is 1~5
Hour.
4. according to the method described in claim 3, it is characterized by: noble metal in step 2), in the noble metal precursor body
Quality accounts for the 20wt% to 60wt% of carbon-carried platinum-based elctro-catalyst gross mass.
5. according to the method described in claim 1, it is characterized by: in step 3), in the NaOH alcoholic solution or KOH alcoholic solution
Mass concentration be 3%~10%；The alcoholic solvent includes ethylene glycol, glycerine or propylene glycol.
6. according to the method described in claim 1, it is characterized by: sealed reaction vessel heating method is outer heat in step 4)
Or interior heat；The acid solution includes HNO3Aqueous solution, H2SO4Aqueous solution or HCL aqueous solution；The acid solution concentration used is
0.1-3.0mol/L。
7. according to the method described in claim 6, it is characterized by: the reaction vessel used is salable resistance to height in step 4)
Pressure vessel, including stainless steel high pressure sealing reaction vessel, polytetrafluoroethylene (PTFE) high pressure sealing reaction vessel etc..
8. according to the method described in claim 1, it is characterized by: filter type includes natural filtration, low pressure mistake in step 5)
Filter, pressure filtration etc.；The deionized water temperature of washing filter cake should be 20 DEG C~100 DEG C；Drying mode includes vacuum drying, air blast
Dry, freeze-drying etc..
9. the carbon-carried platinum-based electricity that the preparation method of carbon-carried platinum-based elctro-catalyst of any of claims 1-8 is prepared
Catalyst.
10. carbon-carried platinum-based catalyst prepared by preparation method of any of claims 1-8 is fired in proton exchange membrane
The application in battery is expected, including the application in hydrogen-air fuel cell catalyst and direct alcohol fuel cell.
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