CN109273725A - Poly- metal phthalocyanine composition, Its Preparation Method And Use - Google Patents
Poly- metal phthalocyanine composition, Its Preparation Method And Use Download PDFInfo
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- CN109273725A CN109273725A CN201810941421.2A CN201810941421A CN109273725A CN 109273725 A CN109273725 A CN 109273725A CN 201810941421 A CN201810941421 A CN 201810941421A CN 109273725 A CN109273725 A CN 109273725A
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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
- 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
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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
- H01M4/96—Carbon-based electrodes
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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 embodiment of the present application provides a kind of poly- metal phthalocyanine composition, Its Preparation Method And Use, the preparation method includes: uniformly to mix conductive carbon, metallic compound, catalyst component, the component containing amino group with the component containing anhydride group, heating, make the metallic compound, the component containing amino group and the component containing anhydride group that polymerization reaction occur under the action of catalyst component, the poly- metallic compound thin layer of a stable structure is formed in conductive carbon surface, obtains the poly- metal phthalocyanine composition.The poly- metal phthalocyanine composition of the application has high oxygen reduction catalytic activity, methanol tolerance performance and cyclical stability: stronger Me-N4The latent active of active site and poly- metal phthalocyanine composition has been obviously improved the catalytic performance of poly- metal phthalocyanine composition；More stable poly- metallic compound structure, hence it is evident that enhance the stable circulation performance of poly- metal phthalocyanine composition.It is cathode assembling into fuel cell using poly- metal phthalocyanine composition of the invention, performance is better than existing catalyst.
Description
Technical field
The invention relates to field of new energy technologies more particularly to a kind of poly- metal phthalocyanine compositions, its preparation side
Method and application thereof.
Background technique
Develop the new energy technologies such as fuel cell, is the effective way for solving human society energy crisis and environmental degradation.
However, fuel cell is limited, expensive with precious metals pt catalyst resource, it is the key that restrict fuel cell scale institute
?.Therefore, the technology that the low cost and high performance inexpensive catalyst of design and development becomes urgent need to resolve in the prior art is asked
Topic.
Summary of the invention
In view of the above problems, the application provides a kind of poly- metal phthalocyanine composition, Its Preparation Method And Use, to solve
The expensive problem of precious metals pt catalyst.
In one embodiment of the application, a kind of preparation method of poly- metal phthalocyanine composition, the preparation method are provided
It include: that conductive carbon, metallic compound, catalyst component, the component containing amino group and the component containing anhydride group is uniform
Mixing is heated so as to the conductive carbon, metallic compound, catalyst component, the component containing amino group and contain anhydride group
Component occur polymerization reaction, obtain the poly- metal phthalocyanine composition.
Optionally, the metallic compound includes transistion metal compound, the transistion metal compound be selected from iron, cobalt,
Or mixtures thereof manganese, nickel, compound of copper, the compound of the iron include ferrous sulfate, frerrous chloride, ferrous nitrate, sulfuric acid
Or mixtures thereof ferrous ammonium, ferric oxalate, ferric sulfate, ferric trichloride, ferric nitrate, ferric acetate, ferric acetyl acetonade；The chemical combination of the cobalt
Object includes or mixtures thereof cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt oxalate, cobalt acetate, acetylacetone cobalt；The compound of the manganese
Including or mixtures thereof manganese sulfate, manganese chloride, manganese nitrate, manganese oxalate, manganese acetate, manganese acetylacetonate；The compound packet of the nickel
Include or mixtures thereof nickel sulfate, nickel chloride, nickel nitrate, nickel oxalate, nickel acetate, nickel acetylacetonate；The compound of the copper includes
Or mixtures thereof copper sulphate, copper chloride, copper nitrate, cupric oxalate, copper acetate, acetylacetone copper.
Optionally, the metallic compound and conductive carbon mass ratio are 0.1~2:1；The catalyst component and conductive carbonaceous
Amount is than being 0.1~10:1；The component containing amino group and conductive carbon mass ratio are 0.1~20:1；It is described to contain acid anhydrides
The component and conductive carbon mass ratio of group are 0.02~2:1.
Optionally, the catalyst component is selected from ammonium molybdate；The group containing amino group is selected from urea；It is described containing
The group of anhydride group is selected from pyromellitic acid anhydride.
Optionally, the heating is so that the conductive carbon, metallic compound, catalyst component, the component containing amino group
Polymerization reaction occurs with the component containing anhydride group to further comprise by the conductive carbon, metallic compound, catalyst component, contain
There is the component of amino group to be heated to melting with the component containing anhydride group, molten liquid is transferred in microwave reactor rapidly
Bring it about polymerization reaction.
Optionally, the conductive carbon is or mixtures thereof spherical, linear.
Optionally, described to be uniformly mixed into one of direct dry mixed, solvent wet-mixing, ball milling mixing or several
Kind, the temperature of the heating is not less than 130 DEG C, and the Microwave Emulsifier-Free Polymerization reaction time is 0-1h, the power setting of microwave reactor
For greater than 100W.
Optionally, the metallic compound, catalyst component, the component containing amino group and the component containing anhydride group
In the Surface Creation polymerized phthalocyanine metal layer of the conductive carbon, the marginal texture of the polymerized phthalocyanine metal is style of opening.
A kind of poly- metal phthalocyanine composition is provided in another embodiment of the application, the poly- metal phthalocyanine composition is adopted
It is prepared with any of the above-described method.
The above-mentioned poly- metal phthalocyanine composition of one kind is provided in the another embodiment of the application to urge as fuel battery negative pole
The purposes of agent.
Compared with prior art, the invention has the characteristics that:
By by conductive carbon, metallic compound, catalyst component, the component containing amino group and containing the group of anhydride group
Divide uniformly mixing, heating, to form metal phthalocyanine polymer shell in conductive carbon surface, the structure is with hyperoxia reduction catalysts
Activity and methanol tolerance performance, the latent active with stronger Me-N4 active site and poly- metal phthalocyanine composition, are obviously improved
The stable circulation performance of poly- metal phthalocyanine composition is cathode assembling into fuel electricity using poly- metal phthalocyanine composition of the invention
Pond, performance are better than business 20wt%Pt/C catalyst.
As by poly- metal phthalocyanine composition made from the embodiment of the present invention with using FePC as shell, using conductive carbon as core
FePc@CB core-shell structure comparison it is found that poly- metal phthalocyanine composition made from the embodiment of the present invention have higher hydrogen reduction
Be catalyzed catalytic activity, methanol tolerance performance and stable circulation performance, using poly- metal phthalocyanine composition of the invention as cathode assembling at
Fuel cell, performance are also better than FePc CB core-shell structure, and reason is likely to be poly- FePC compared in phthalocyanine iron powder
The site Fe-N4 latent active is stronger, structure is more stable.
Certainly, any technical solution for implementing the embodiment of the present application does not need to reach simultaneously above all excellent necessarily
Point.
Detailed description of the invention
Fig. 1 is the synthetic route chart of poly- FePC in one embodiment of the application.
Fig. 2 is the image of the poly- metal phthalocyanine composition of the preparation of the embodiment of the present application 1 under a scanning electron microscope.
Fig. 3 be the embodiment of the present application 1 prepare poly- metal phthalocyanine composition and business 20wt%Pt/C catalyst oxygen also
The comparison diagram of former polarization curve.
Fig. 4 is that poly- metal phthalocyanine composition prepared by the embodiment of the present application 1 tests the oxygen of front and back also by cyclical stability
Former polarization curve.
Fig. 5 is that poly- metal phthalocyanine composition prepared by the embodiment of the present application 1 is made respectively with business 20wt%Pt/C catalyst
The performance test curve graph of monocell is assembled for fuel battery cathod catalyst.
Fig. 6 is poly- metal phthalocyanine composition prepared by the embodiment of the present application 12 and business 20wt%Pt/C catalyst in 0.1M
Polarization curves of oxygen reduction figure in KOH electrolyte.
Fig. 7 is that poly- metal phthalocyanine composition prepared by the embodiment of the present application 12 is made respectively with business 20wt%Pt/C catalyst
The performance test curve graph of monocell is assembled for fuel battery cathod catalyst.
Specific embodiment
In order to make those skilled in the art more fully understand the technical solution in the embodiment of the present application, below in conjunction with the application
Test data and attached drawing in embodiment, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that
Described embodiment is only the embodiment of the present application a part of the embodiment, instead of all the embodiments.Implemented based on the application
The embodiment of the present application all should belong in embodiment in example, those of ordinary skill in the art's every other embodiment obtained
The range of protection.
In one embodiment of the application, a kind of preparation method of poly- metal phthalocyanine composition, the preparation method are provided
It include: that conductive carbon, metallic compound, catalyst component, the component containing amino group and the component containing anhydride group is uniform
Mixing is heated so as to the conductive carbon, metallic compound, catalyst component, the component containing amino group and contain anhydride group
Component occur polymerization reaction, obtain the poly- metal phthalocyanine composition.Conductive carbon, catalyst component, contains ammonia at metallic compound
The component of base group is uniformly mixed with the component containing anhydride group, heating, to form a side in conductive carbon surface aggregate
The poly- metal phthalocyanine shell of edge structure opening type is to get o-pFePc@CB core-shell structure.By taking iron compound as an example, marginal texture is opened
The synthetic route for putting the poly- FePC of type is as shown in Figure 1.
Optionally, the synthetic route of the poly- metal phthalocyanine composition of one embodiment of the application be one kettle way, i.e., by conductive carbon,
Metallic compound, catalyst component, the component containing amino group are mixed simultaneously with the component containing anhydride group and are heated, but
Each component can also be mixed according to different order, and the application is without restriction herein.The poly- metal phthalocyanine group that the application is prepared
The post-processing such as pickling, secondary high-temperature, pore-creating can be carried out by closing object.
Optionally, the metallic compound includes transistion metal compound and nontransition metal compound, the transition gold
Belong to compound and be selected from or mixtures thereof iron, cobalt, manganese, nickel, the compound of copper, the compound of the iron includes ferrous sulfate, chlorination
Ferrous iron, ferrous nitrate, iron ammonium sulfate, ferric oxalate, ferric sulfate, ferric trichloride, ferric nitrate, ferric acetate, ferric acetyl acetonade or its
Mixture or other contain the compound of iron.The compound of the cobalt includes cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt oxalate, vinegar
Or mixtures thereof sour cobalt, acetylacetone cobalt or other contain the compound of cobalt.The compound of the manganese includes manganese sulfate, chlorination
Or mixtures thereof manganese, manganese nitrate, manganese oxalate, manganese acetate, manganese acetylacetonate or other contain the compound of manganese.The change of the nickel
Conjunction object includes or mixtures thereof nickel sulfate, nickel chloride, nickel nitrate, nickel oxalate, nickel acetate, nickel acetylacetonate or other contain nickel
Compound.The compound of the copper include copper sulphate, copper chloride, copper nitrate, cupric oxalate, copper acetate, acetylacetone copper or its
Mixture or other contain the compound of copper.
Optionally, the metallic compound and conductive carbon mass ratio are 0.1~2:1；The catalyst component and conductive carbonaceous
Amount is than being 0.1~10:1；The component containing amino group and conductive carbon mass ratio are 0.1~20:1；It is described to contain acid anhydrides
The component and conductive carbon mass ratio of group are 0.02~2:1.It is formed in poly- metal phthalocyanine composition made from the embodiment of the present application
Me-N4 (Me represents metal) structure, is active site, the atomic percentage content of the metal (Me) in metallic compound is 0~
3at%, but can not exist in the form of+divalent or+trivalent for 0, Me；The atomic percentage content of N is 0~20at%, but is not 0, N
Mainly with the presence of the species such as pyridine N, pyrroles N.Me couples to form Me-N4 structure with N.
Optionally, the catalyst component is selected from ammonium molybdate or other are suitable for the substance of catalyst component；It is described to contain ammonia
The group of base group is selected from urea or other substances for containing amino group；The group containing anhydride group is selected from equal benzene four
Formic acid dianhydride or other contain the substance of anhydride group.
Optionally, the heating is so that the conductive carbon, metallic compound, catalyst component, the component containing amino group
Polymerization reaction occurs with the component containing anhydride group to further comprise by the conductive carbon, metallic compound, catalyst component, contain
There is the component of amino group to be heated to melting with the component containing anhydride group, molten liquid is transferred in microwave reactor rapidly
Bring it about polymerization reaction.
Optionally, the conductive carbon is or mixtures thereof spherical, linear, spherical carbon material include EC600JD, EC300J,
One of Vulcan XC72, BP2000 etc. or more, the linear carbon material include that carbon nanotube, carbon fiber, carbon are received
One of rice stick etc. or more.
Optionally, described to be uniformly mixed into one of direct dry mixed, solvent wet-mixing, ball milling mixing or several
Kind, the temperature of the heating is not less than 130 DEG C, and the Microwave Emulsifier-Free Polymerization reaction time is 0-1h, the power setting of microwave reactor
For greater than 100W.
Optionally, the metallic compound, catalyst component, the component containing amino group and the component containing anhydride group
In the Surface Creation polymerized phthalocyanine metal layer of the conductive carbon, the marginal texture of the polymerized phthalocyanine metal is style of opening.
A kind of poly- metal phthalocyanine composition is provided in another embodiment of the application, the poly- metal phthalocyanine composition is adopted
It is prepared with any of the above-described method.
The above-mentioned poly- metal phthalocyanine composition of one kind is provided in the another embodiment of the application to urge as fuel battery negative pole
The purposes of agent.
The specific implementation of the embodiment of the present application is further illustrated below with reference to the embodiment of the present application and attached drawing.
Embodiment 1
1) preparation of poly- metal phthalocyanine composition
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:
The mass ratio of 0.2:0.6:1 uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor rapidly bring it about it is poly-
Reaction is closed to get poly- metal phthalocyanine composition, which is o-pFePc@CB core-shell structure carbon, wherein core
For conductive carbon, shell is that green vitriol, urea with pyromellitic acid anhydride react generation under the catalytic action of ammonium molybdate
FePC polymer, shell is coated with core.Image such as Fig. 2 institute of the poly- metal phthalocyanine composition in scanning electron microscope
Show.
2) the structure composition analysis of poly- metal phthalocyanine composition
It is analysed in depth in conjunction with structure composition of a variety of characterization techniques to poly- metal phthalocyanine composition: XPS (X-ray
Photoelectron spectroscopy, ray photoelectron spectroscopic analysis, abbreviation XPS) analysis obtains the combination of poly- metal phthalocyanine
The atom content ratio of object surface Fe, N are 8.5:1, theoretical ratio 8:1 of the ratio very close to poly- phthalocyanine iron molecule.In addition,(Mo&4&ssbauer spectrum) test result shows that poly- metal phthalocyanine composition has double-peak feature, this all illustrates poly- gold
Belonging to phthalocyanine composition includes Fe-N4Cellular construction.
3) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, using three-electrode system respectively to poly- metal phthalocyanine composition (o-pFePc@CB) and business 20wt%
Pt/C catalyst carries out electrochemical property test, and platinized platinum is to electrode, and mercury/mercury oxide is reference electrode, and 0.1M KOH is electrolysis
Liquid.As shown in Fig. 3 polarization curve, hydrogen reduction test result shows poly- metal phthalocyanine composition (o-pFePc@CB) and business
Under carrying capacity the same terms of 20wt%Pt/C catalyst, poly- metal phthalocyanine composition (o-pFePc@CB) polarization curves of oxygen reduction
Half wave potential is~0.89V (vs.RHE (Reversible Hydrogen Electrode, reversible hydrogen electrode)), more existing
Business 20wt%Pt/C catalyst (~0.85 V) improves 30mV or more.In addition, 0.1M methanol is added in the electrolytic solution, it is right respectively
Poly- metal phthalocyanine composition (o-pFePc@CB) and business 20wt%Pt/C catalyst carry out methanol tolerance performance test: poly- metal phthalein
Polarization curve essentially coincides cyanines composition (o-pFePc@CB) before and after adding methanol, illustrates poly- metal phthalocyanine composition (o-
PFePc@CB) have very excellent methanol tolerance performance, and business 20wt%Pt/C catalyst be added methanol after performance significantly
Decaying.
Further, cyclical stability test is carried out to the poly- metal phthalocyanine composition of preparation (o-pFePc@CB): will prepared
Good working electrode is placed in the 0.1M KOH electrolyte of oxygen saturation, carries out the test of initial oxygen reducing property；Hereafter, by work
Make electrode and carries out 0.02~1.22V (vs.RHE) full potential range scans, electrical potential scan rate 50mV/s, scan round 1000
After circle, the evaluation and test of hydrogen reduction performance is carried out again.The hydrogen reduction pole of the poly- metal phthalocyanine composition (o-pFePc@CB) in circulation front and back
Change curve to be not much different and (reduce only~5mV before half wave potential relatively recycles after circulation), as shown in figure 4, illustrating the poly- metal of preparation
Phthalocyanine composition (o-pFePc@CB) has preferable stable circulation performance.
Next, respectively using poly- metal phthalocyanine composition (o-pFePc@CB) and business 20wt%Pt/C as cathode catalysis
Agent is assembled into fuel-cell single-cell, and test results are shown in figure 5, and poly- metal phthalocyanine composition (o-pFePc@CB) shows
Power density reach 117mW/cm2, hence it is evident that power density (the power density 84mW/cm better than business 20wt%Pt/C2), it says
It is bright to use poly- metal phthalocyanine composition (o-pFePc@CB) that there is better performance as the fuel cell of cathod catalyst.
Embodiment 2
1) poly- metal phthalocyanine composition (o-pFePc@CB) when shell (o-pFePc) and core (conductive carbon) mass ratio are 0.2:1
Preparation
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.1:
The mass ratio of 0.1:0.1:0.05 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor makes its hair rapidly
Raw polymerization reaction forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@
CB core-shell structure.Remove the part of loss, the mass ratio of o-pFePc and CB (conductive carbon) is 0.2:1.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, chemical property is carried out to poly- metal phthalocyanine composition (o-pFePc@CB) material using three-electrode system
Test, platinized platinum are to electrode, and mercury/mercury oxide is reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition (o-pFePc@CB) shows excellent oxygen reduction catalytic activity, oxygen
Reduction polarization curve half wave potential is~0.88V (vs.RHE), hence it is evident that is better than business 20wt%Pt/C.In addition, in 0.1M KOH
The oxygen reduction activity variation that poly- metal phthalocyanine composition (o-pFePc@CB) is tested in 0.1M methanol front and back is added in electrolyte, as a result
It has been shown that, poly- metal phthalocyanine composition (o-pFePc@CB) activity do not decay, and illustrate it with excellent methanol tolerance performance.Into one
The poly- metal phthalocyanine composition prepared (o-pFePc@CB) working electrode is carried out the test of long-time cyclical stability, followed by step
Half wave potential relatively recycles preceding reduction only~5mV after ring and 20%Pt/C is reduced and reached 200mV or more, illustrates that it has shown compared with Pt/C
The excellent stability of catalyst.
Embodiment 3
1) preparation of poly- metal phthalocyanine composition (o-pFePc@CB) when o-pFePc and conductive carbon mass ratio are 20:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:2:10:
The mass ratio of 20:2 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor brings it about polymerization instead rapidly
It answers, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB nucleocapsid knot
Structure.By controlling the additional amount of conductive carbon, realize that the ratio that o-pFePc and CB mass ratio is 20:1 regulates and controls.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, the poly- metal phthalocyanine composition of preparation shows excellent oxygen reduction catalytic activity, hydrogen reduction pole
Changing curve half wave potential is~0.884V (vs.RHE), hence it is evident that is better than business 20wt%Pt/C.In addition, being electrolysed in 0.1M KOH
The oxygen reduction activity variation that poly- metal phthalocyanine composition is tested in 0.1M methanol front and back is added in liquid, the results show that poly- metal phthalocyanine
The activity of composition does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine group that will be prepared
Close object working electrode and carry out the test of long-time cyclical stability, reduce only~5mV before half wave potential relatively recycles after circulation and 20%
Pt/C, which is reduced, reaches 200mV or more, illustrates that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 4
1) preparation of poly- metal phthalocyanine composition when iron compound and conductive carbon mass ratio are 0.1:1
EC300J conductive carbon, iron compound (green vitriol), ammonium molybdate, urea and pyromellitic acid anhydride are pressed
The mass ratio of 1:0.1:0.2:0.6:1 uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor makes it rapidly
Polymerization reaction occurs, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-
PFePc@CB core-shell structure.By the additional amount of iron compound in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.888V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 5
1) preparation of poly- metal phthalocyanine composition when iron compound and conductive carbon mass ratio are 2:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:2:0.2:
The mass ratio of 0.6:1 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor brings it about polymerization instead rapidly
It answers, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB nucleocapsid knot
Structure.By the additional amount of iron compound in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.886V (vs.RHE), hence it is evident that is better than business 20wt%Pt/C catalyst.In addition, being electrolysed in 0.1M KOH
The oxygen reduction activity variation that poly- metal phthalocyanine composition is tested in 0.1M methanol front and back is added in liquid, the results show that poly- metal phthalocyanine
The activity of composition does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine group that will be prepared
Close object working electrode and carry out the test of long-time cyclical stability, reduce only~5mV before half wave potential relatively recycles after circulation and 20%
Pt/C, which is reduced, reaches 200mV or more, illustrates that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 6
1) preparation of poly- metal phthalocyanine composition when ammonium molybdate and conductive carbon mass ratio are 0.1:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:
The mass ratio of 0.1:0.6:1 uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor rapidly bring it about it is poly-
Reaction is closed, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB core
Shell structure.By the additional amount of ammonium molybdate in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.887V (vs.RHE), hence it is evident that is better than business 20wt%Pt/C catalyst.In addition, being electrolysed in 0.1M KOH
The oxygen reduction activity variation that poly- metal phthalocyanine composition is tested in 0.1M methanol front and back is added in liquid, the results show that poly- metal phthalocyanine
The activity of composition does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine group that will be prepared
Close object working electrode and carry out the test of long-time cyclical stability, reduce only~5mV before half wave potential relatively recycles after circulation and 20%
Pt/C, which is reduced, reaches 200mV or more, illustrates that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 7
1) preparation of poly- metal phthalocyanine composition when ammonium molybdate and conductive carbon mass ratio are 10:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:10:
The mass ratio of 0.6:1 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor brings it about polymerization instead rapidly
It answers, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB nucleocapsid knot
Structure.By the additional amount of ammonium molybdate in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.883V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 8
1) preparation of poly- metal phthalocyanine composition when urea and conductive carbon mass ratio are 0.1:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are uniformly pressed into 1:0.6:
The mass ratio of 0.2:0.1:1 mixes, and is heated to melting, and molten liquid is transferred in microwave reactor brings it about polymerization instead rapidly
It answers, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB nucleocapsid knot
Structure.By the additional amount of urea in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.887V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 9
1) preparation of poly- metal phthalocyanine composition when urea and conductive carbon mass ratio are 20:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:
The mass ratio of 0.2:20:1 uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor rapidly bring it about it is poly-
Reaction is closed, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB core
Shell structure.By the additional amount of urea in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.889V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 10
1) preparation of poly- metal phthalocyanine composition when pyromellitic acid anhydride and conductive carbon mass ratio are 0.02:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:
The mass ratio of 0.2:0.6:0.02 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor makes its hair rapidly
Raw polymerization reaction forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@
CB core-shell structure.By the additional amount of pyromellitic acid anhydride in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.885V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C catalyst.In addition, being electrolysed in 0.1M KOH
The oxygen reduction activity variation that poly- metal phthalocyanine composition is tested in 0.1M methanol front and back is added in liquid, the results show that poly- metal phthalocyanine
The activity of composition does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine group that will be prepared
Close object working electrode and carry out the test of long-time cyclical stability, reduce only~5mV before half wave potential relatively recycles after circulation and 20%
Pt/C, which is reduced, reaches 200mV or more, illustrates that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 11
1) preparation of poly- metal phthalocyanine composition when pyromellitic acid anhydride and conductive carbon mass ratio are 2:1
EC300J conductive carbon, green vitriol, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:
The mass ratio of 0.2:0.6:2 uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor rapidly bring it about it is poly-
Reaction is closed, forms the poly- FePC shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pFePc@CB core
Shell structure.By the additional amount of pyromellitic acid anhydride in control precursor mixture, ratio regulation is realized.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.89V (vs.RHE), hence it is evident that is better than business 20wt% Pt/C.In addition, being added in 0.1M KOH electrolyte
The oxygen reduction activity variation of poly- metal phthalocyanine composition is tested before and after 0.1M methanol, the results show that poly- metal phthalocyanine composition
Activity does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition prepared is worked
Electrode carries out the test of long-time cyclical stability, reduces only~5mV before half wave potential relatively recycles after circulation and business 20wt%
Pt/C catalyst degradation reaches 200mV or more, illustrates that it has shown the stability excellent compared with business 20wt%Pt/C catalyst.
Embodiment 12
1) preparation of FePc@CB core-shell structure when shell is FePC
EC300J conductive carbon is uniformly mixed with business phthalocyanine iron powder by the mass ratio of 1:1, the wet process in alcohol solvent
Ball milling 0.5 hour to get FePc@CB core-shell structure.
2) the electrochemical property test analysis of FePc@CB core-shell structure
At room temperature, electrochemical property test is carried out to FePc@CB core-shell structure using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, as a result as shown in fig. 6, FePc@CB core-shell structure shows excellent oxygen reduction catalytic activity, hydrogen reduction polarizes
Curve half wave potential is~0.87V (vs.RHE), improves 20mV or more compared with business 20wt% Pt/C (~0.85V), but be lower than o-
The poly- metal phthalocyanine composition of pFePc@CB nucleocapsid (~0.89V).In addition, before adding 0.1M methanol in 0.1M KOH electrolyte
The oxygen reduction activity variation of poly- metal phthalocyanine composition is tested afterwards, the results show that the activity of poly- metal phthalocyanine composition does not decline
Subtract, illustrates it with excellent methanol tolerance performance.Further, fuel cell list electricity is assembled by cathod catalyst of FePc@CB
Pond, test results are shown in figure 7, and the power density shown is~100mW/cm2, better than the power of business 20wt%Pt/C
Density (84mW/cm2) but be inferior to power density (117 mW/cm of o-pFePc@CB2)。
Embodiment 13
1) preparation of poly- metal phthalocyanine composition (o-pCoPc@CB)
EC300J conductive carbon, acetylacetone cobalt, ammonium molybdate, urea and pyromellitic acid anhydride are pressed into 1:0.6:0.2:
The mass ratio of 0.6:1 uniformly mixes, and is heated to melting, and molten liquid is transferred in microwave reactor brings it about polymerization instead rapidly
It answers, forms the poly- Cobalt Phthalocyanine shell of a marginal texture style of opening in conductive carbon surface aggregate to get o-pCoPc@CB nucleocapsid knot
Structure.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition (o-pCoPc@CB)
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.88V (vs.RHE), is better than business 20wt%Pt/C catalyst.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 14
1) preparation of poly- metal phthalocyanine composition (o-pMnPc@CB)
By EC300J conductive carbon, manganese acetate, ammonium molybdate, urea and pyromellitic acid anhydride by 1:0.6:0.2:0.6:1's
Mass ratio uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor brings it about polymerization reaction rapidly, is leading
Electrical carbon surface aggregate forms the poly- manganese phthalocyanine shell of a marginal texture style of opening to get o-pMnPc@CB core-shell structure.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition (o-pMnPc@CB)
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.87V (vs.RHE), is better than business 20wt%Pt/C catalyst.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C is urged
Agent, which reduces, reaches 200mV or more, illustrates that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 15
1) preparation of poly- metal phthalocyanine composition (o-pNiPc@CB)
By EC300J conductive carbon, manganese chloride, ammonium molybdate, urea and pyromellitic acid anhydride by 1:0.6:0.2:0.6:1's
Mass ratio uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor brings it about polymerization reaction rapidly, is leading
Electrical carbon surface aggregate forms the poly- manganese phthalocyanine shell of a marginal texture style of opening to get o-pMnPc@CB core-shell structure.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition (o-pNiPc@CB)
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.875V (vs.RHE), is better than business 20wt%Pt/C catalyst.In addition, in 0.1M KOH electrolyte
The oxygen reduction activity variation that poly- metal phthalocyanine composition is tested in 0.1M methanol front and back is added, the results show that poly- metal phthalocyanine combines
The activity of object does not decay, and illustrates it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition that will be prepared
Working electrode carries out the test of long-time cyclical stability, reduces only~5mV before half wave potential relatively recycles after circulation and 20%Pt/C
It reduces and reaches 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
Embodiment 16
1) preparation of poly- metal phthalocyanine composition (o-pCuPc@CB)
By EC300J conductive carbon, copper nitrate, ammonium molybdate, urea and pyromellitic acid anhydride by 1:0.6:0.2:0.6:1's
Mass ratio uniformly mixes, and is heated to melting, molten liquid is transferred in microwave reactor brings it about polymerization reaction rapidly, is leading
Electrical carbon surface aggregate forms the poly- CuPc shell of a marginal texture style of opening to get o-pCuPc@CB core-shell structure.
2) the electrochemical property test analysis of poly- metal phthalocyanine composition (o-pCuPc@CB)
At room temperature, electrochemical property test is carried out to poly- metal phthalocyanine composition using three-electrode system, platinized platinum is to electricity
Pole, mercury/mercury oxide are reference electrode, and 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s, the results showed that, poly- metal phthalocyanine composition shows excellent oxygen reduction catalytic activity, polarization curves of oxygen reduction
Half wave potential is~0.88V (vs.RHE), is better than business 20wt%Pt/C catalyst.In addition, adding in 0.1M KOH electrolyte
0.1M methanol front and back is added to test the oxygen reduction activity variation of poly- metal phthalocyanine composition, the results show that poly- metal phthalocyanine composition
Activity do not decay, illustrate it with excellent methanol tolerance performance.Further, the poly- metal phthalocyanine composition work that will be prepared
Make electrode and carry out the test of long-time cyclical stability, half wave potential relatively recycles preceding reduction only~5mV after circulation and 20%Pt/C drops
Down to 200mV or more, illustrate that it has shown the stability excellent compared with Pt/C catalyst.
In conclusion by by conductive carbon, metallic compound, catalyst component, the component containing amino group with containing acid
The component of anhydride group uniformly mixes, and heating makes the metallic compound, the group containing amino group under the action of catalyst component
Divide and polymerization reaction occurs with the component containing anhydride group, forms the poly- metallic compound of a stable structure in conductive carbon surface
Thin layer obtains the poly- metal phthalocyanine composition.The poly- metal phthalocyanine composition of the application has high oxygen reduction catalytic activity, resists
Methanol performance and cyclical stability: the latent active of stronger Me-N4 active site and poly- metal phthalocyanine composition is obviously improved
The catalytic performance of poly- metal phthalocyanine composition；More stable poly- metallic compound structure, hence it is evident that enhance poly- metal phthalocyanine group
Close the stable circulation performance of object.It is cathode assembling into fuel cell using poly- metal phthalocyanine composition of the invention, performance is better than quotient
Industry 20wt%Pt/C catalyst.
As by poly- metal phthalocyanine composition made from the embodiment of the present invention with using FePC as shell, using conductive carbon as core
FePc@CB core-shell structure comparison it is found that poly- metal phthalocyanine composition made from the embodiment of the present invention have higher hydrogen reduction
Be catalyzed catalytic activity, methanol tolerance performance and stable circulation performance, using poly- metal phthalocyanine composition of the invention as cathode assembling at
Fuel cell, performance are also better than FePc CB core-shell structure, and reason is likely to be poly- FePC compared in phthalocyanine iron powder
The site Fe-N4 latent active is stronger, structure is more stable.
Certainly, any technical solution for implementing the embodiment of the present application does not need to reach simultaneously above all excellent necessarily
Point.
Finally, it should be noted that above embodiments are only to illustrate the technical solution of the embodiment of the present application, rather than it is limited
System；Although the application is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: its
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is equal
Replacement；And these are modified or replaceed, each embodiment technical solution of the application that it does not separate the essence of the corresponding technical solution
Spirit and scope.
Claims (10)
1. a kind of preparation method of poly- metal phthalocyanine composition, which is characterized in that the preparation method includes: by conductive carbon, gold
Belong to compound, catalyst component, the component containing amino group uniformly to mix with the component containing anhydride group, heat so that described
Conductive carbon, metallic compound, catalyst component, the component containing amino group polymerize instead with the component containing anhydride group
It answers, obtains the poly- metal phthalocyanine composition.
2. preparation method according to claim 1, which is characterized in that the metallic compound includes transition metal compound
Object, the transistion metal compound are selected from or mixtures thereof iron, cobalt, manganese, nickel, the compound of copper, and the compound of the iron includes
Ferrous sulfate, frerrous chloride, ferrous nitrate, iron ammonium sulfate, ferric oxalate, ferric sulfate, ferric trichloride, ferric nitrate, ferric acetate, second
Or mixtures thereof acyl acetone iron；The compound of the cobalt includes cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt oxalate, cobalt acetate, acetyl
Or mixtures thereof acetone cobalt；The compound of the manganese includes manganese sulfate, manganese chloride, manganese nitrate, manganese oxalate, manganese acetate, levulinic
Or mixtures thereof ketone manganese；The compound of the nickel includes nickel sulfate, nickel chloride, nickel nitrate, nickel oxalate, nickel acetate, acetylacetone,2,4-pentanedione
Or mixtures thereof nickel；The compound of the copper includes copper sulphate, copper chloride, copper nitrate, cupric oxalate, copper acetate, acetylacetone copper
Or mixtures thereof.
3. preparation method according to claim 1, which is characterized in that the metallic compound is with conductive carbon mass ratio
0.1~2:1；The catalyst component and conductive carbon mass ratio are 0.1~10:1；The component and conductive carbon containing amino group
Mass ratio is 0.1~20:1；The component containing anhydride group and conductive carbon mass ratio are 0.02~2:1.
4. preparation method according to claim 1, which is characterized in that the catalyst component is selected from ammonium molybdate；It is described containing
The group of amino group is selected from urea；The group containing anhydride group is selected from pyromellitic acid anhydride.
5. preparation method according to claim 1, which is characterized in that the heating is so that the conductive carbon, metal compound
It further comprises by institute that with the component containing anhydride group polymerization reaction, which occurs, for object, catalyst component, the component containing amino group
Conductive carbon, metallic compound, catalyst component, the component containing amino group and the component containing anhydride group is stated to be heated to melting
Melt, molten liquid is transferred in microwave reactor brings it about polymerization reaction rapidly.
6. preparation method according to claim 1, which is characterized in that the conductive carbon is or mixtures thereof spherical, linear.
7. preparation method according to claim 1, which is characterized in that described to be uniformly mixed into direct dry mixed, solvent
One or more of wet-mixing, ball milling mixing, the temperature of the heating are not less than 130 DEG C, when the Microwave Emulsifier-Free Polymerization reacts
Between be 0-1h, the power setting of microwave reactor is greater than 100W.
8. preparation method according to claim 1, which is characterized in that the metallic compound, contains amino at catalyst component
The component of group and Surface Creation polymerized phthalocyanine metal layer of the component containing anhydride group in the conductive carbon, the polymerization phthalein
The marginal texture of cyanines metal is style of opening.
9. a kind of poly- metal phthalocyanine composition, which is characterized in that the poly- metal phthalocyanine composition uses such as claim 1 to 8
Described in any item methods are prepared.
10. the purposes that poly- metal phthalocyanine composition described in a kind of claim 11 is used as fuel battery cathod catalyst.
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Application publication date: 20190125 |