CN104241664B - A kind of PtM/M '-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction and preparation method thereof - Google Patents
A kind of PtM/M '-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction and preparation method thereof Download PDFInfo
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- CN104241664B CN104241664B CN201410475939.3A CN201410475939A CN104241664B CN 104241664 B CN104241664 B CN 104241664B CN 201410475939 A CN201410475939 A CN 201410475939A CN 104241664 B CN104241664 B CN 104241664B
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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
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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 relates to a kind of PtM/M'PPy C eelctro-catalyst for fuel cell oxygen reduction reaction, this PtM/M'PPy C eelctro-catalyst includes the composition of following mass percent: activity component metal Pt15.4～36.5%, auxiliary agent M1.7～9.3%, and remaining is carrier.Described PtM/M'PPy C eelctro-catalyst is by active component presoma and auxiliary agent presoma one step being joined in the conductive carrier mixing suspension with reducing agent, use pulse microwave assistant chemical reducing process Pt metal and M to be supported in conductive carrier, prepare by precipitating, filter, wash, being vacuum dried.Compared with prior art, operating process of the present invention is simple, and the PtM/M'PPy C electrocatalyst particles prepared is evenly distributed, and size is little, and oxygen reduction reaction catalysis activity is high, can be used for fuel cell field.
Description
Technical field
The invention belongs to fuel cell technology and novel energy resource material technology field, relate to a kind of eelctro-catalyst and system thereof
Preparation Method, especially relate to a kind of for fuel cell oxygen reduction reaction PtM/M'-PPy-C eelctro-catalyst and
Preparation method.
Background technology
At present, Proton Exchange Membrane Fuel Cells (PEMFC) technology has enjoyed the extensive concern of countries in the world, its
Can play an increasingly important role at following new energy field.Although every technology of PEMFC has become
In maturation, there is the prospect of large-scale commercial application, and for enabling PEMFC to realize merchandized handling early,
Various countries' researcher is being devoted to the research of associated materials, tries hard to reduce PEMFC cost, improves relevant
The performance of material, the most just includes the research of high-performance electric catalyst.Eelctro-catalyst is the crucial material of PEMFC
Material, the preparation method of the active component of catalyst, carrier and catalyst largely can directly affect PEMFC
Performance and cost.Therefore, preparation activity is high, the performance improving fuel cell is had by the catalyst of good stability
Very important effect.
Now, the cathod catalyst for fuel cell is mainly Pt/C catalyst, due to the kinetics of hydrogen reduction
Slowly, even on the highest Pt surface of activity, also can there is the open circuit polarization of about 200mV in process.
The alloying of Pt catalyst can improve the speed of oxygen reduction reaction to a certain extent, and reduces hydrodynamic voltages damage
Lose.And Pt/C eelctro-catalyst as cathode catalyst material time, carbon support material at electromotive force higher than 0.207V (vs
NHE), time, it may occur that electrochemical oxidation, cause the migration of Pt granule or come off, thus causing catalyst failure.
In recent years research shows, polypyrrole (PPy) class transition metal carrier M-PPy-C (M=Fe, Co, Ni)
Having special structure, M (II) and N or O can form the coordinate bond with oxygen reduction activity, thus right
Molecular oxygen shows good catalysis activity.It addition, polypyrrole also has stablizes non-noble metal characteristic, be conducive to
Improve the stability in the large of catalyst.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of particle size little,
There is higher oxygen reduction reaction catalysis activity, it is possible to for the PtM/M'-PPy-C of fuel cell oxygen reduction reaction
Eelctro-catalyst.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of PtM/M'-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction, this PtM/M'-PPy-C
Eelctro-catalyst includes the composition of following mass percent: activity component metal Pt15.4～36.5%, auxiliary agent
M1.7～9.3%, remaining is carrier.
Described auxiliary agent M is one or more simple substance in Fe, Co, Ni.
Described carrier is PPy class transition metal carrier M '-PPy-C, preferably Fe-PPy-C, Co-PPy-C or
Ni-PPy-C, PPy class transition metal carrier M '-PPy-C can use preparation method well known in the art to make, as
Use document R.Bashyam, P.Zelenay, A class of non-precious metal composite catalysts for
The method that fuel cells.Nature 2006,443: 63 records is prepared.
A kind of preparation method of the PtM/M'-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction, the method
It it is the mixing suspension that active component presoma and auxiliary agent presoma one step are joined conductive carrier and reducing agent
In, use pulse microwave assistant chemical reducing process Pt metal and M to be reduced from presoma, and be supported on carrier
On, then through precipitating, filter, wash, being vacuum dried, i.e. prepare PtM/M'-PPy-C eelctro-catalyst, specifically wrap
Include following steps:
(1) it is 1 by the mass ratio of carrier Yu reducing agent: (200～800), carrier is joined in reductant solution,
Ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1 by the mol ratio of Pt in M in auxiliary agent presoma and active component presoma: (1～3), will live
Property component presoma join together with auxiliary agent presoma step (1) prepare suspending liquid A in, ultrasonic agitation is equal
Even, regulation solution ph is 8～12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, uses pulse microwave auxiliaryization
Learn reducing process to react, after reaction terminates, treat that solution temperature is down to room temperature, through precipitating, filter, wash, very
Empty dry, i.e. prepare PtM/M'-PPy-C eelctro-catalyst.
In auxiliary agent presoma described in step (2), M with the mol ratio of M ' in the carrier described in step (1) is
1: (2～4).
The described soluble inorganic salt that active component presoma is Pt metal, preferably chloroplatinic acid, platinum nitrate.
The described soluble organic salts that auxiliary agent presoma is M or soluble inorganic salt, the solubility of described M
Inorganic salt preferably nitrate, sulfate or chloride, the preferred acetate of soluble organic salts of described M.
Described reducing agent is one or more in formaldehyde, acetaldehyde, ethylene glycol, glycerol or sodium borohydride.
The operating condition using pulse microwave assistant chemical reducing process described in step (4) is: to microwave reactor
In be passed through inert protective gas, the working time of microwave reactor is 5～50s, and the relaxation time is 50～300s, micro-
Wave power is 0-5～3kW, and microwave repeat function number of times is 5～30 times.
Vacuum drying temperature described in step (4) is 60～120 DEG C, and vacuum is-0.09～-0.1Mpa, is dried
Time is 6～12h.
Compared with prior art, the invention have the characteristics that:
(1) using pulse microwave assistant chemical reducing process to be prepared, operational approach is simple, and reaction condition is gentle,
Reaction rate is fast, can realize being carried on carrier active component and auxiliary agent the most simultaneously；
(2) the PtM/M'-PPy-C electrocatalyst particles size preparing gained is little, even particle size distribution, and heat is steady
Qualitative good, have good to oxygen reduction reaction catalytic performance.
Accompanying drawing explanation
Fig. 1 is the PtM/M'-PPy-C eelctro-catalyst linear sweep voltammetry test spectrogram prepared by embodiment 1；
Fig. 2 is the transmission electron microscope (TEM) of the PtM/M'-PPy-C eelctro-catalyst prepared by embodiment 1
Spectrogram；
Fig. 3 is cyclic voltammetric (CV) spectrogram of the PtM/M'-PPy-C eelctro-catalyst prepared by embodiment 2；
Fig. 4 is the PtM/M'-PPy-C eelctro-catalyst linear sweep voltammetry test spectrogram prepared by embodiment 2；
Fig. 5 is the PtM/M'-PPy-C eelctro-catalyst linear sweep voltammetry test spectrogram prepared by embodiment 3；
Fig. 6 is the transmission electron microscope (TEM) of the PtM/M'-PPy-C eelctro-catalyst prepared by embodiment 3
Spectrogram；
Fig. 7 is the PtM/M'-PPy-C eelctro-catalyst linear sweep voltammetry test spectrogram prepared by embodiment 4；
Fig. 8 is the X-ray diffraction spectrogram (XRD) of the PtM/M'-PPy-C eelctro-catalyst prepared by embodiment 4；
Fig. 9 is the PtM/M'-PPy-C eelctro-catalyst linear sweep voltammetry test spectrogram prepared by embodiment 5；
Figure 10 is the X-ray diffraction spectrogram (XRD) of the PtM/M'-PPy-C eelctro-catalyst prepared by embodiment 5.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
The present embodiment, uses pulse microwave assistant chemical reduction method for preparing Pt Ni/Co-PPy-C eelctro-catalyst
(Pt: Ni: Co mol ratio 3: 1: 4, it is 20% that PtNi accounts for the percentage ratio of catalyst gross mass, then to account for catalyst total for Pt
The percentage ratio of quality is 18.2%, and it is 1.8% that Ni accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 300 by the mass ratio of support C o-PPy-C Yu ethylene glycol, support C o-PPy-C is joined
In ethylene glycol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 3 by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, chloroplatinic acid is added together with nickel nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Co in Ni and support C o-PPy-C in nickel nitrate
It is 1: 4 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 20s, and the relaxation time is 100s, and microwave power is 1kW,
Microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction；After question response terminates, will
Solution temperature is down to room temperature, takes out solution through precipitating, filter, washing, and obtains sample, and by sample 80 DEG C,
Vacuum is-0.1MPa, is vacuum dried 8h, i.e. prepares PtNi/Co-PPy-C eelctro-catalyst.
The PtNi/Co-PPy-C eelctro-catalyst that the present embodiment is prepared gained carries out linear sweep voltammetry test, test
Condition: sweep limits is 0.05～1.2V (vs.RHE), scanning speed is 5mV s-1, electrode rotating speed is 1600rpm,
Solution is the 0.1mol L that oxygen is saturated-1HClO4Solution, test result is as shown in Figure 1.
As seen from Figure 2, the PtNi/Co-PPy-C eelctro-catalyst of the gained electric current under 0.9V voltage is prepared
Density reaches 1.0mA/cm2, it is shown that good catalytic performance.
Fig. 2 show the present embodiment and prepares the TEM spectrogram of gained PtNi/Co-PPy-C eelctro-catalyst, by Fig. 2
It can be seen that prepare the even particle size of the PtNi/Co-PPy-C eelctro-catalyst of gained, good dispersion, substantially
Not unity phenomenon, the mean diameter of granule is about 2.5nm.
Embodiment 2:
The present embodiment, uses pulse microwave assistant chemical reduction method for preparing Pt Ni/Co-PPy-C eelctro-catalyst
(Pt: Ni: Co mol ratio 1: 1: 2, it is 20% that PtNi accounts for the percentage ratio of catalyst gross mass, then to account for catalyst total for Pt
The percentage ratio of quality is 15.4%, and it is 4.6% that Ni accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 200 by the mass ratio of support C o-PPy-C Yu ethylene glycol, support C o-PPy-C is joined
In ethylene glycol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 1 by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, chloroplatinic acid is added together with nickel nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Co in Ni and support C o-PPy-C in nickel nitrate
It is 1: 2 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 20s, and the relaxation time is 100s, and microwave power is 1kW,
Microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction；After question response terminates, will
Solution temperature is down to room temperature, takes out solution through precipitating, filter, washing, and obtains sample, and by sample 80 DEG C,
Vacuum is-0.1MPa, is vacuum dried 8h, i.e. prepares PtNi/Co-PPy-C eelctro-catalyst.
The PtNi/Co-PPy-C eelctro-catalyst that this enforcement is prepared gained is circulated volt-ampere test, test condition:
Sweep limits is 0.05～1.15V (vs.RHE), and sweep speed is 50mV s-1, test curve is as shown in Figure 3.
Can be calculated by Fig. 3 and learn, the electrochemical surface area of the PtNi/Co-PPy-C eelctro-catalyst preparing gained reaches
To 72m2/ g, has bigger active area.
The PtNi/Co-PPy-C eelctro-catalyst that the present embodiment is prepared gained carries out linear sweep voltammetry test, test
Condition: sweep limits is 0.05～1.2V (vs.RHE), scanning speed is 5mV s-1, electrode rotating speed is 1600rpm,
Solution is the 0.1mol L that oxygen is saturated-1HClO4Solution, test result as shown in Figure 4, prepares gained
PtNi/Co-PPy-C eelctro-catalyst electric current density under 0.9V voltage reaches 1.1mA/cm2, it is shown that good
Catalytic performance.
Embodiment 3:
The present embodiment, uses pulse microwave assistant chemical reduction method for preparing Pt Fe/Co-PPy-C eelctro-catalyst
(Pt: Fe: Co mol ratio 3: 1: 4, it is 20% that PtFe accounts for the percentage ratio of catalyst gross mass, then to account for catalyst total for Pt
The percentage ratio of quality is 18.3%, and it is 1.7% that Fe accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 300 by the mass ratio of support C o-PPy-C Yu ethylene glycol, support C o-PPy-C is joined
In ethylene glycol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 3 by the mol ratio of Pt in Fe in ferric nitrate and chloroplatinic acid, chloroplatinic acid is added together with ferric nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Co in Fe and support C o-PPy-C in ferric nitrate
It is 1: 4 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 20s, and the relaxation time is 100s, and microwave power is 1kW,
Microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction；After question response terminates, will
Solution temperature is down to room temperature, takes out solution through precipitating, filter, washing, and obtains sample, and by sample 60 DEG C,
Vacuum is-0.09MPa, is vacuum dried 12h, i.e. prepares PtFe/Co-PPy-C eelctro-catalyst.
The PtFe/Co-PPy-C eelctro-catalyst that the present embodiment is prepared gained carries out linear sweep voltammetry test, test
Condition: sweep limits is 0.05～1.2V (vs.RHE), scanning speed is 5mV s-1, electrode rotating speed is 1600rpm,
Solution is the 0.1mol L that oxygen is saturated-1HClO4Solution, test result is as it is shown in figure 5, prepare gained
PtFe/Co-PPy-C eelctro-catalyst electric current density under 0.9V voltage reaches 1.2mA/cm2, it is shown that good
Catalytic performance.
Fig. 6 show the present embodiment and prepares the TEM spectrogram of gained PtFe/Co-PPy-C eelctro-catalyst, by Fig. 6
It can be seen that prepare the even particle size of the PtFe/Co-PPy-C eelctro-catalyst of gained, good dispersion, substantially
Not unity phenomenon, the mean diameter of granule is about 2.4nm.
Embodiment 4:
The present embodiment, uses pulse microwave assistant chemical reduction method for preparing Pt Ni/Co-PPy-C eelctro-catalyst
(Pt: Ni: Co mol ratio 3: 1: 4, it is 20% that PtNi accounts for the percentage ratio of catalyst gross mass, then to account for catalyst total for Pt
The percentage ratio of quality is 18.2%, and it is 1.8% that Ni accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 200 by the mass ratio of support C o-PPy-C Yu glycerol, support C o-PPy-C is joined
In glycerol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 3 by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, chloroplatinic acid is added together with nickel nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Co in Ni and support C o-PPy-C in nickel nitrate
It is 1: 4 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 20s, and the relaxation time is 100s, and microwave power is 1kW,
Microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction；After question response terminates, will
Solution temperature is down to room temperature, takes out solution through precipitating, filter, washing, and obtains sample, and by sample 80 DEG C,
Vacuum is-0.09MPa, is vacuum dried 8h, i.e. prepares PtNi/Co-PPy-C eelctro-catalyst.
The PtNi/Co-PPy-C eelctro-catalyst that the present embodiment is prepared gained carries out linear sweep voltammetry test, test
Condition: sweep limits is 0.05～1.2V (vs.RHE), scanning speed is 5mV s-1, electrode rotating speed is 1600rpm,
Solution is the 0.1mol L that oxygen is saturated-1HClO4Solution, test result is as it is shown in fig. 7, prepare gained
PtNi/Co-PPy-C eelctro-catalyst electric current density under 0.9V voltage reaches 1.2mA/cm2, it is shown that good
Catalytic performance.
Fig. 8 is the XRD test spectrogram that gained PtNi/Co-PPy-C eelctro-catalyst is prepared in this enforcement, test condition:
Operating pressure is 40kV, and sweep limits is 20 °～90 °, and scanning speed is 6 °/min.
In Fig. 8 first peak occur in 2 θ=25 ° be C (002), Pt (111), Pt (200), Pt (220),
2 corresponding respectively for Pt (311) θ angle value are 40 °, 46 °, 68 °, 81 °, the wherein peak of Pt (111)
The strongest, illustrate that in the PtNi/Co-PPy-C eelctro-catalyst prepared, Pt granule is mainly face-centered cubic crystal formation.
Embodiment 5:
The present embodiment, employing pulse microwave assistant chemical reduction method for preparing Pt Ni/Fe-PPy-C eelctro-catalyst (Pt: Ni:
Fe mol ratio 3: 1: 4, it is 40% that PtNi accounts for the percentage ratio of catalyst gross mass, then Pt accounts for catalyst gross mass
Percentage ratio is 30.7%, and it is 9.3% that Ni accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 200 by the mass ratio of carrier Fe-PPy-C Yu glycerol, carrier Fe-PPy-C is joined third
In triol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 3 by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, chloroplatinic acid is added together with nickel nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Fe in Ni and carrier Fe-PPy-C in nickel nitrate
It is 1: 4 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 10, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 50s, and the relaxation time is 300s, and microwave power is
0.5kW, microwave repeat function number of times is 30 times, starts microwave reactor, carries out reduction reaction；Question response is tied
Shu Hou, is down to room temperature by solution temperature, and taking-up solution, through precipitating, filter, washing, obtains sample, and by sample
60 DEG C, vacuum be-0.09MPa, be vacuum dried 12h, i.e. prepare PtNi/Fe-PPy-C eelctro-catalyst.
The PtNi/Fe-PPy-C eelctro-catalyst that the present embodiment is prepared gained carries out linear sweep voltammetry test, test
Condition: sweep limits is 0.05～1.2V (vs.RHE), scanning speed is 5mV s-1, electrode rotating speed is 1600rpm,
Solution is the 0.1mol L that oxygen is saturated-1HClO4Solution, test result is as it is shown in figure 9, prepare gained
PtNi/Fe-PPy-C eelctro-catalyst electric current density under 0.9V voltage reaches 0.9mA/cm2, it is shown that good
Catalytic performance.
Figure 10 is the XRD test spectrogram that gained PtNi/Fe-PPy-C eelctro-catalyst is prepared in this enforcement, test condition:
Operating pressure is 40kV, and sweep limits is 20 °～90 °, and scanning speed is 6 °/min.
In figure first peak occur in 2 θ=25 ° be C (002), Pt (111), Pt (200), Pt (220),
2 corresponding respectively for Pt (311) θ angle value are 40 °, 47 °, 67 °, 82 °, the wherein peak of Pt (111)
The strongest, illustrate that in the PtNi/Co-PPy-C eelctro-catalyst prepared, Pt granule is mainly face-centered cubic crystal formation.
Embodiment 6:
The present embodiment, employing pulse microwave assistant chemical reduction method for preparing Pt Fe/Co-PPy-C eelctro-catalyst (Pt: Fe:
Co mol ratio 3: 1: 3, it is 40% that PtNi accounts for the percentage ratio of catalyst gross mass, then Pt accounts for catalyst gross mass
Percentage ratio is 36.5%, and it is 3.5% that Ni accounts for the percentage ratio of catalyst gross mass), concrete preparation method is as follows:
(1) it is 1: 800 by the mass ratio of support C o-PPy-C Yu ethylene glycol, support C o-PPy-C is joined
In glycerol, ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1: 3 by the mol ratio of Pt in Fe in ferric nitrate and chloroplatinic acid, chloroplatinic acid is added together with ferric nitrate
Enter to step (1) in the suspending liquid A prepared, wherein, Co in Fe and support C o-PPy-C in ferric nitrate
It is 1: 3 that mol ratio controls, and ultrasonic agitation is uniform, and regulation solution ph is 8, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, is passed through inert nitrogen gas,
Draining air, the working time arranging microwave reactor is 5s, and the relaxation time is 50s, and microwave power is 3kW,
Microwave repeat function number of times is 5 times, starts microwave reactor, carries out reduction reaction；After question response terminates, by molten
Liquid temp is down to room temperature, takes out solution through precipitating, filter, washing, and obtains sample, and by sample 120 DEG C,
Vacuum is-0.09MPa, is vacuum dried 6h, i.e. prepares PtFe/Co-PPy-C eelctro-catalyst.
Claims (13)
1. the PtM/M '-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction, it is characterised in that
This PtM/M '-PPy-C eelctro-catalyst includes the composition of following mass percent: activity component metal
Pt15.4～36.5%, auxiliary agent M1.7～9.3%, remaining is carrier；
The preparation method of described PtM/M '-PPy-C eelctro-catalyst is: by active component presoma and auxiliary agent forerunner
Body one step joins in the mixing suspension of conductive carrier and reducing agent, uses pulse microwave assistant chemical reducing process
Pt metal and M are reduced from presoma, and are supported on carrier, then through precipitating, filter, washing, vacuum
It is dried, i.e. prepares PtM/M '-PPy-C eelctro-catalyst, specifically include following steps:
(1) it is 1:(200～800 by the mass ratio of carrier Yu reducing agent), carrier is joined in reductant solution,
Ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1:(1～3 by the mol ratio of Pt in M in auxiliary agent presoma and active component presoma), will live
Property component presoma join together with auxiliary agent presoma step (1) prepare suspending liquid A in, ultrasonic agitation is equal
Even, regulation solution ph is 8～12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, uses pulse microwave auxiliaryization
Learn reducing process to react, after reaction terminates, treat that solution temperature is down to room temperature, through precipitating, filter, wash, very
Empty dry, i.e. prepare PtM/M '-PPy-C eelctro-catalyst.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 1
Catalyst, it is characterised in that described auxiliary agent M is one or more simple substance in Fe, Co, Ni.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 1
Catalyst, it is characterised in that described carrier is PPy class transition metal carrier M '-PPy-C.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 3
Catalyst, it is characterised in that described PPy class transition metal carrier M '-PPy-C is Fe-PPy-C, Co-PPy-C
Or the one in Ni-PPy-C.
5. urge for the PtM/M '-PPy-C electricity of fuel cell oxygen reduction reaction as claimed in claim 1 for one kind
The preparation method of agent, it is characterised in that the method is active component presoma and auxiliary agent presoma one step to be added
In the conductive carrier mixing suspension with reducing agent, use pulse microwave assistant chemical reducing process by Pt metal
Reduce from presoma with M, and be supported on carrier, then through precipitating, filter, wash, be vacuum dried, i.e.
Prepare PtM/M '-PPy-C eelctro-catalyst, specifically include following steps:
(1) it is 1:(200～800 by the mass ratio of carrier Yu reducing agent), carrier is joined in reductant solution,
Ultrasonic agitation is uniform, prepares suspending liquid A；
(2) it is 1:(1～3 by the mol ratio of Pt in M in auxiliary agent presoma and active component presoma), will live
Property component presoma join together with auxiliary agent presoma step (1) prepare suspending liquid A in, ultrasonic agitation is equal
Even, regulation solution ph is 8～12, prepares suspension B；
(3) the suspension B that step (2) prepares is placed in microwave reactor, uses pulse microwave auxiliaryization
Learn reducing process to react, after reaction terminates, treat that solution temperature is down to room temperature, through precipitating, filter, wash, very
Empty dry, i.e. prepare PtM/M '-PPy-C eelctro-catalyst.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 5
The preparation method of catalyst, it is characterised in that M and step (1) in the auxiliary agent presoma described in step (2)
In described carrier, the mol ratio of M ' is 1:(2～4).
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 5
The preparation method of catalyst, it is characterised in that the described soluble inorganic that active component presoma is Pt metal
Salt.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 7
The preparation method of catalyst, it is characterised in that the soluble inorganic salt of described Pt metal is chloroplatinic acid or nitric acid
Platinum.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 5
The preparation method of catalyst, it is characterised in that the described soluble organic salts that auxiliary agent presoma is M or solvable
Property inorganic salt.
A kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction the most according to claim 9
The preparation method of catalyst, it is characterised in that the soluble inorganic salt of described M be nitrate, sulfate or
Chloride, the soluble organic salts of described M is acetate.
11. a kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction according to claim 5
The preparation method of catalyst, it is characterised in that described reducing agent be formaldehyde, acetaldehyde, ethylene glycol, glycerol or
One or more in sodium borohydride.
12. a kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction according to claim 5
The preparation method of catalyst, it is characterised in that the employing pulse microwave assistant chemical reducing process described in step (3)
Operating condition be: being passed through inert protective gas in microwave reactor, the working time of microwave reactor is 5～50
S, the relaxation time is 50～300s, and microwave power is 0.5～3kW, and microwave repeat function number of times is 5～30 times.
13. a kind of PtM/M '-PPy-C electricity for fuel cell oxygen reduction reaction according to claim 5
The preparation method of catalyst, it is characterised in that the vacuum drying temperature described in step (3) is 60～120 DEG C,
Vacuum is-0.09～-0.1MPa, and drying time is 6～12h.
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| CN112397732A (en) * | 2020-11-13 | 2021-02-23 | 上海海事大学 | ORR catalyst material and preparation method and application thereof |
| CN112687895B (en) * | 2020-12-25 | 2022-04-12 | 苏州擎动动力科技有限公司 | Catalyst and preparation method thereof |
| CN115863669A (en) * | 2023-02-09 | 2023-03-28 | 江苏皇冠新材料科技有限公司 | Method for preparing nano particle catalyst by liquid phase deposition and application thereof |
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| US4954474A (en) * | 1988-02-18 | 1990-09-04 | Tanaka Kikinzoku Kogyo K.K. | Process for preparing catalysts by alloying metals on supports |
| CN101722049A (en) * | 2009-11-25 | 2010-06-09 | 武汉理工大学 | Catalyst modified by proton conductor and using conductive polymer as carrier and preparation method thereof |
| CN103372467A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Support for electrode catalyst and method of manufacturing the same, electrode catalyst and fuel cell |
| CN103855411A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Catalyst of fuel cell and application of catalyst |
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| US4954474A (en) * | 1988-02-18 | 1990-09-04 | Tanaka Kikinzoku Kogyo K.K. | Process for preparing catalysts by alloying metals on supports |
| CN101722049A (en) * | 2009-11-25 | 2010-06-09 | 武汉理工大学 | Catalyst modified by proton conductor and using conductive polymer as carrier and preparation method thereof |
| CN103372467A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Support for electrode catalyst and method of manufacturing the same, electrode catalyst and fuel cell |
| CN103855411A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Catalyst of fuel cell and application of catalyst |
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