CN101716530A - Catalyst using composite polymer as carrier - Google Patents
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- CN101716530A CN101716530A CN200910272918A CN200910272918A CN101716530A CN 101716530 A CN101716530 A CN 101716530A CN 200910272918 A CN200910272918 A CN 200910272918A CN 200910272918 A CN200910272918 A CN 200910272918A CN 101716530 A CN101716530 A CN 101716530A
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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
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- 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 invention discloses a catalyst using a composite polymer as a carrier. The composite polymer is jointly formed by an electricity conducting polymer and a proton conducting polymer. The preparation method of the catalyst comprises: dispersing the proton conducting polymer in an aqueous solution of an alcohol, adding the electricity conducting polymer monomer into the solution according to a mass ratio of the proton conducting polymer and the electricity conducting polymer monomer of 0.1-100:1, and fully stirring the solution to obtain a dispersion; adding a polymerization initiator of the electricity conducting polymer monomer into the prepared dispersion to perform a polymerization reaction under a condition of a constant temperature between 0 and 10 DEG C for 2 to 8 hours till the monomer is completely polymerized to obtain a composite polymer; and dispersing the composite polymer in the aqueous solution of the alcohol, adding a saline solution of a metal precursor according to a mass ratio of the electricity conducting polymer monomer to metal catalyst particles of 0.1-100:1, fully stirring the mixed solution in the presence of N2, He or Ar and heating the mixed solution to 90 to 10 DEG C to perform refluxing for 30 to 60 minutes to obtain the catalyst. The catalyst has electricity conducting and proton conducting functions, high corrosion resistance and high durability, and as catalyst metal particles, has a big bonding force with the carrier.
Description
Technical field
The present invention relates to a kind of with the Catalysts and its preparation method of composite polymer as carrier.Institute's invention catalyst has conduction and leads the proton dual-use function, has good chemical stability, has boundless potential using value at industrial circles such as photoelectricity, batteries.
Technical background
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell is called for short PEMFC) directly is converted into electric energy to the chemical energy that is stored in fuel and the oxidant, there is not environmental pollution, not limited by Carnot cycle, energy conversion efficiency is far above hot machine.Therefore, will be with a wide range of applications at aspects such as distributed power station, electric motor car and compact powers.The PEMFC catalyst is extensive use of carbon supported platinum catalyst or carbon carries the platinum-ruthenium alloys catalyst, and the latter is mainly used in DMFC (DMFC), to strengthen the ability that the catalyst anti-carbon monoxide is poisoned.
Catalyst carrier material has very important important function with the same performance to catalyst performance of catalyst platinum isoreactivity material.It is not only formed in structure and is playing the part of aspect mass transfer for active material provides the huge specific area and the role of structure electron channel, can also produce tangible auxiliary catalysis effect to the performance of major catalyst with very important carrier effect.At present, the catalyst carrier in the fuel cell mostly is carbon black, as the Vulcan XC72 of Cabot company production.But the utilization rate of Pt is not high among the Pt/C of preparation, is usually less than 20%.This is because a large amount of platinum or platinum alloy particles is deposited in the micropore of porous carbon black, can not contact with proton conductor, therefore is unfavorable for forming more phase reactions district.In addition, the electrochemical stability of carbon black is relatively poor, and the electrochemical environment of fuel battery inside is more abominable, makes carbon black that electrochemical corrosion take place easily, has promoted the loss or the reunion of platinum or platinum alloy particles.And the mechanical strength of carbon black is not high yet.These have all limited the catalyst based application in fuel cell of Pt.
Conducting polymer has good electric conductivity, and common conducting polymer has polypyrrole (PPy), polyaniline (PAn), polythiophene (PTh) etc.(PAn) has the long-chain conjugated structure as conductive polymer polyanilinc, and proton can reversible doping on the polyaniline molecule long-chain, makes polyaniline have the performance of electronic conduction.In addition, polyaniline also has excellent antioxygenic property under acid condition.Domestic existing conductive polymer applications is in the report of fuel cell at present.Make the binding agent modification one-dimensional nano carbon as human electrically conductive polyanilines such as Wuhan University of Technology's wood scholar's spring, and then in metal catalyst particles such as its area load Pt, preparation fuel-cell catalyst (ZL200510018287.1).
Under the acid condition of work of Proton Exchange Membrane Fuel Cells, lead the proton polymer and have the reasonable proton ability of leading usually, if in order to modified catalyst, can make up proton channel preferably, help forming the more required three-phase reaction interface of multiple fuel cell electrochemical reaction.For this reason, the inventor adopts the sub-polymer of the conduction cell catalyst carrier that acts as a fuel to make up the electron channel of catalyst (layer), and simultaneously, it is polymer-modified that the nanocatalyst metallic particles is led proton, makes to have the dual-use function catalyst that conducts electricity and lead proton.
At present, conducting polymer is not arranged as yet and lead the relevant report of proton composite polymer as catalyst carrier and synthetic catalyst.
Summary of the invention
It is the fuel-cell catalyst of carrier by conducting polymer with leading the composite polymer that the proton polymer constitutes that the object of the invention aims to provide a kind of.Purpose of the present invention also provides this composite polymer and Preparation of catalysts method.
Composite polymer provided by the invention is compared with background technology as the fuel-cell catalyst of carrier, has the following advantages: 1) catalyst carrier possesses excellent corrosion resistance, and favorable conductive and lead the proton dual-use function; 2) conducting polymer and lead the proton polymer and can improve adhesion between catalyst metal particles and carrier as binding agent makes the durability of catalyst be improved.
Realize the technical scheme of the object of the invention:
A kind of is the fuel-cell catalyst of carrier with the composite polymer, it is characterized in that, described composite polymer is by conducting polymer and leads the proton polymer and constitute jointly.
Wherein, the described proton polymer of leading is selected from perfluorinated sulfonic resin, SPSF resinoid, sulfonated polyphenyl sulfide resin (SPPS), sulfonated polyphenyl and imidazoles, sulfonated polyimide resin (SPIs), sulfonated polystyrene ion exchange resin (SPS) or sulfonated polyether-ether-ketone resin (SPEEK).
Described conducting polymer is polyaniline, polypyrrole or polythiophene.
Composite polymer of the present invention is the preparation method of the fuel-cell catalyst of carrier, it is characterized in that, prepare conducting polymer and the composite polymer of leading the proton polymer earlier, the metal supported catalyst particle is to the composite polymer surface then, and concrete preparation process is as follows:
Step 1: will lead the proton polymer dispersed in alcohol solution, and add the conducting polymer monomer then, and lead the mass ratio 0.1～100: 1 of proton polymer and conducting polymer monomer, and fully stir, and make dispersion liquid;
Step 2: the polymerization initiator of conducting polymer monomer is joined in the made dispersion liquid of step 1, maintain the temperature at 0～10 ℃, react and made monomer polymerization complete in 2～8 hours, make composite polymer;
Step 3: the composite polymer of step 2 preparation is scattered in the alcohol solution, add the metal precursor salting liquid, the mass ratio of conducting polymer monomer and metal catalyst particles is 0.1～100: 1, under N2, He or Ar protection, fully stir, 90～100 ℃ added hot reflux 30～60 minutes, made the fuel-cell catalyst that composite polymer is a carrier;
Alcohol is 0.5～100: 1 with the mass ratio of water in the wherein said alcohol solution, and alcohol is methyl alcohol, ethanol, propyl alcohol, ethylene glycol or isopropyl alcohol; Described conducting polymer is selected from polyaniline, polypyrrole or polythiophene; The described proton polymer of leading is selected from perfluorinated sulfonic resin, the SPSF resinoid, the sulfonated polyphenyl sulfide resin, sulfonated polyphenyl and imidazoles, sulfonated polyimide resin, sulfonated polystyrene ion exchange resin or sulfonated polyether-ether-ketone are set described polymerization initiator and are made up of oxidant and Bronsted acid or are made of oxidant separately, wherein oxidant is an Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ferric trichloride, dichromic acid amine or hydrogen peroxide, Bronsted acid comprises inorganic acid and organic acid two classes, inorganic acid is a hydrochloric acid, nitric acid, sulfuric acid or perchloric acid, organic acid are benzene sulfonic acid, DBSA or perfluorinated sulfonic resin; Metal is metal alloy or metal simple-substance in the described metallic catalyst, alloy is MxNy or MxNyOz, wherein x, y, z are each metal quality ratio in the catalyst, its numerical value is respectively the natural number in 0～100, and x+y=100 or x+y+z=100, M, N, O are respectively Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, W or Mo metallic element, and M, N, O are different, and metal simple-substance is Pt, Ru, Pd, Rh, Ir or Os.
Compare with existing carbon supported platinum catalyst, catalyst of the present invention is a kind of multifunction catalyst, has following advantage:
1. conducting polymer such as polyaniline are very stable under sour environment, conduct electricity very well, and resistance to corrosion is strong, can improve the service life of catalyst;
2. leading the proton polymer itself is exactly proton conductor, makes the composite polymer of preparation have conduction and function of guiding protons preferably simultaneously;
3. metal nanoparticle can be scattered in polymer surfaces preferably, and forms adhesion preferably with carrier, and the durability of catalyst is improved.
Description of drawings:
Fig. 1 is the transmission electron microscope picture (TEM) of the composite polymer loaded Pt catalyst of polyaniline and Nafion formation.
Pt particle diameter≤5nm wherein, average grain diameter 2.8nm, and better dispersed.
The specific embodiment
Below by embodiment in detail the present invention is described in detail:
Embodiment 1
Get in the mixed solution that 6ml Nafion (7wt%) joins the isopropyl alcohol of 100ml and water, the mass ratio of isopropyl alcohol and water is 3: 1, adds 90wt% aniline solution 0.5g again after stirring 5～10min, stirs 20～40min.The hydrochloric acid solution 25ml that with ammonium persulfate 0.6g and concentration is 1mol/L again joins in the dispersion liquid, stirs 6 hours down at 5 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polyaniline and Nafion.It is distributed in the mixed solution of 150ml isopropyl alcohol and water, and the mass ratio of isopropyl alcohol and water is 3: 1, adds the H of 4g/L
2PtCl
680ml regulates PH=10 with KOH, feeds He, adds hot reflux 50min at 98 ± 2 ℃, through cleaning, drying, obtains the Pt catalyst.Pt particle diameter≤5nm wherein, average grain diameter 2.8nm, and better dispersed, the results are shown in accompanying drawing 1.
Embodiment 2
Get in the mixed solution that 10ml SPSF (9wt%) joins the ethylene glycol of 200ml and water, the mass ratio of ethylene glycol and water is 2: 1, adds 90wt% aniline solution 2g again after stirring 6～10min, stirs 30～40min.The sulfuric acid solution 15ml that with potassium bichromate 1g and concentration is 1mol/L again joins in the dispersion liquid, stirs 7 hours down at 0 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polyaniline and SPSF.It is distributed in the mixed solution of 200ml ethylene glycol and water, and the mass ratio of ethylene glycol and water is 2: 1, adds the H of 6g/L
2PtCl
640ml, 6g/LRuCl
340ml regulates PH=9 with KOH, feeds N
2, add hot reflux 40min at 95 ± 2 ℃, through cleaning, drying, obtain the PtRu catalyst.Wherein PtRu average grain diameter 4.1nm, and dispersiveness better.
Embodiment 3
Get in the mixed solution that 8ml sulfonated polyphenyl thioether (6wt%) joins the isopropyl alcohol of 100ml and water, the mass ratio of isopropyl alcohol and water is 1: 2, adds 95wt% pyrroles's solution 4g again after stirring 5～10min, stirs 30min.The benzene sulfonic acid solution 30ml that with hydrogen peroxide 2.5g and concentration is 2mol/L again joins in the dispersion liquid, stirs 5 hours down at 10 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polypyrrole and sulfonated polyphenyl thioether.It is distributed in the mixed solution of 250ml isopropyl alcohol and water, and the mass ratio of isopropyl alcohol and water is 1: 2, adds the H of 5g/L
2PtCl
660ml, the IrCl of 5g/L
330ml regulates PH=11 with NaOH, feeds He, adds hot reflux 50min at 90 ± 5 ℃, through cleaning, drying, obtains the PtIr catalyst.Wherein PtIr average grain diameter 4.0nm, and dispersiveness better.
Embodiment 4
Get in the mixed solution of second alcohol and water that 12ml sulfonated polyphenyl and imidazoles (8wt%) join 250ml, the mass ratio of second alcohol and water is 3: 1, adds 90wt% pyrroles's solution 2g again after stirring 10～15min, stirs 20～40min.The salpeter solution 20ml that with dichromic acid amine 0.5g and concentration is 1.5mol/L again joins in the dispersion liquid, stirs 3 hours down at 5 ℃, after filtration, alcohol washes, makes the composite polymer that is made of polypyrrole and sulfonated polyphenyl and imidazoles.It is distributed in the mixed solution of 200ml second alcohol and water, and the mass ratio of second alcohol and water is 3: 1, adds the H of 4g/L
2PtCl
680ml, the Co (NO of 4g/L
3)
255ml regulates PH=10 with KOH, feeds Ar, adds hot reflux 35min at 95 ± 5 ℃, through cleaning, drying, obtains the PtCo catalyst.Wherein PtCo average grain diameter 3.7nm, and dispersiveness better.
Embodiment 5
Get in the mixed solution of second alcohol and water that 7ml sulfonated polyimide (10wt%) joins 200ml, the mass ratio of second alcohol and water is 3: 2, adds 80wt% thiophene solution 0.8g again after stirring 5～10min, stirs 30～40min.Again ferric trichloride 3g is joined in the dispersion liquid, stirred 7 hours down at 0 ℃, after filtration, alcohol washes, the composite polymer that constitutes by polythiophene and sulfonated polyimide.It is distributed in the mixed solution of 150ml second alcohol and water, and the mass ratio of second alcohol and water is 3: 2, adds the H of 4g/L
2PtCl
6100ml, the PdCl of 4g/L
260ml regulates PH=9 with NaOH, feeds N
2, add hot reflux 40min at 90 ± 2 ℃, through cleaning, drying, obtain the PtPd catalyst.Wherein PtPd average grain diameter 3.6nm, and dispersiveness better.
Embodiment 6
Get in the mixed solution that 15ml sulfonated polystyrene (6wt%) joins the ethylene glycol of 150ml and water, the mass ratio of ethylene glycol and water is 4: 3, adds 90wt% thiophene solution 3g again after stirring 8～10min, stirs 30min.Again ferric trichloride 6g is joined in the dispersion liquid, stirred 6 hours down, after filtration, alcohol washes, and makes the composite polymer that is made of polythiophene and sulfonated polystyrene at 5 ℃.It is distributed in the mixed solution of 250ml ethylene glycol and water, and the mass ratio of ethylene glycol and water is 2: 1, adds the H of 6g/L
2PtCl
660ml, the PdCl of 6g/L
220ml, the CoCl of 6g/L
230ml regulates PH=10 with KOH, feeds He, adds hot reflux 50min at 95 ± 2 ℃, through cleaning, drying, obtains the PtPdCo catalyst.Wherein PtPdCo average grain diameter 4.9nm, and dispersiveness better.
Embodiment 7
Get in the mixed solution of first alcohol and water that 10ml sulfonated polyether-ether-ketone (9wt%) joins 200ml, the mass ratio of first alcohol and water is 80: 1, adds 90wt% aniline solution 2.5g again after stirring 5～10min, stirs 20～40min.The salpeter solution 30ml that with sodium peroxydisulfate 1.5g and concentration is 1mol/L again joins in the dispersion liquid, stirs 6 hours down at 10 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polyaniline and sulfonated polyether-ether-ketone.It is distributed in the mixed solution of 250ml first alcohol and water, and the mass ratio of first alcohol and water is 80: 1, adds the PdCl of 10g/L
280ml, the FeCl of 10g/L
350ml regulates PH=9 with KOH, feeds He, adds hot reflux 40min at 90 ± 2 ℃, through cleaning, drying, obtains the PdFe catalyst.Wherein PdFe average grain diameter 4.1nm, and dispersiveness better.
Embodiment 8
Get in the mixed solution of second alcohol and water that 8ml Nafion (4wt%) joins 150ml, the mass ratio of second alcohol and water is 4: 1, adds 90wt% pyrroles's solution 1.5g again after stirring 10min, stirs 20～40min.The salpeter solution 20ml that with sodium peroxydisulfate 1.0g and concentration is 1mol/L again joins in the dispersion liquid, stirs 6 hours down at 0 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polypyrrole and Nafion.It is distributed in the mixed solution of 250ml second alcohol and water, and the mass ratio of second alcohol and water is 2: 1, adds the PdCl of 5/L
280ml, the Co (NO of 5/L
3)
260ml, the MnCl of 5/L
260ml regulates PH=10 with KOH, feeds N
2, add hot reflux 40min at 98 ± 2 ℃, through cleaning, drying, obtain the PdCoMn catalyst.Wherein PdCoMn average grain diameter 4.9nm, and dispersiveness better.
Embodiment 9
Get in the mixed solution that 10ml SPSF (6wt%) joins the isopropyl alcohol of 100ml and water, the mass ratio of isopropyl alcohol and water is 1: 1, adds 95wt% pyrroles's solution 0.8g again after stirring 9min, stirs 35～40min.The hydrochloric acid solution 25ml that with hydrogen peroxide 1.7g and concentration is 1mol/L again joins in the dispersion liquid, stirs 6 hours down at 0 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polypyrrole and SPSF.It is distributed in the mixed solution of 150ml isopropyl alcohol and water, and the mass ratio of isopropyl alcohol and water is 1: 1, adds the H of 4g/L
2PtCl
650ml, the RuCl of 4g/L
350ml, the Co (NO of 4g/L
3)
250ml regulates PH=11 with NaOH, feeds He, adds hot reflux 40min at 100 ℃, through cleaning, drying, obtains the PtRuCo catalyst.Wherein PtRuCo average grain diameter 4.6nm, and dispersiveness better.
Embodiment 10
Get in the mixed solution that 5ml sulfonated polyphenyl thioether (7wt%) joins the ethylene glycol of 200ml and water, the mass ratio of ethylene glycol and water is 2: 3, adds 95wt% aniline solution 0.8g again after stirring 5～10min, stirs 20～40min.The perchloric acid solution 25ml that with ammonium persulfate 0.8g and concentration is 1mol/L again joins in the dispersion liquid, stirs 6 hours down at 0 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polyaniline and sulfonated polyphenyl thioether.It is distributed in the mixed solution of 200ml ethylene glycol and water, and the mass ratio of ethylene glycol and water is 2: 3, adds the PdCl of 6g/L
210ml, the IrCl of 6g/L
310ml regulates PH=10 with NaOH, feeds He, adds hot reflux 40min at 98 ± 2 ℃, through cleaning, drying, obtains the PdIr catalyst.Wherein PdIr average grain diameter 3.8nm, and dispersiveness better.
Embodiment 11
Get in the mixed solution of third alcohol and water that 25ml sulfonated polyphenyl and imidazoles (9wt%) join 150ml, the mass ratio of third alcohol and water is 5: 2, adds 95wt% thiophene solution 0.8g again after stirring 5～10min, stirs 25min.Again ferric trichloride 4g is joined in the dispersion liquid, stirred 5 hours down, after filtration, alcohol washes, make the composite polymer that constitutes by polythiophene and sulfonated polyphenyl and imidazoles at 5 ℃.It is distributed in the mixed solution of 150ml third alcohol and water, and the mass ratio of third alcohol and water is 5: 2, adds the H of 7g/L
2PtCl
620ml, the Co (NO of 5g/L
3)
215ml, the Na of 5g/L
2WO
415ml regulates PH=10 with NaOH, feeds Ar, adds hot reflux 40min at 90 ± 2 ℃, through cleaning, drying, obtains the catalyst through PtCoW.Wherein PtCoW average grain diameter 4.8nm, and dispersiveness better.
Embodiment 12
Get in the mixed solution of first alcohol and water that 10ml sulfonated polyimide (10wt%) joins 120ml, the mass ratio of first alcohol and water is 100: 1, adds 95wt% aniline solution 2.0g again after stirring 10min, stirs 20～30min.The sulfuric acid solution 30ml that with potassium peroxydisulfate 1.5g and concentration is 1mol/L again joins in the dispersion liquid, stirs 3 hours down at 10 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polyaniline and sulfonated polyimide.It is distributed in the mixed solution of 250ml first alcohol and water, and the mass ratio of first alcohol and water is 100: 1, adds the PdCl of 6g/L
230ml, 6g/L's, SnCl
320ml regulates PH=10 with NaOH, feeds N
2, add hot reflux 60min at 95 ℃, through cleaning, drying, obtain the PdSn catalyst.Wherein PdSn average grain diameter 3.8nm, and dispersiveness better.
Embodiment 13
Get in the mixed solution that 15ml sulfonated polystyrene (4wt%) joins the isopropyl alcohol of 100ml and water, the mass ratio of isopropyl alcohol and water is 3: 2, adds 95wt% thiophene solution .0.1g again after stirring 6min, stirs 30～40min.Again ferric trichloride 0.8g is joined in the dispersion liquid, stirred 7 hours down, after filtration, alcohol washes, and makes the composite polymer that is made of polythiophene and sulfonated polystyrene at 5 ℃.It is distributed in the mixed solution of 250ml isopropyl alcohol and water, and the mass ratio of isopropyl alcohol and water is 3: 2, adds the H of 6g/L
2PtCl
660ml, the FeCl of 4g/L
320ml regulates PH=9 with KOH, feeds He, adds hot reflux 40min at 98 ± 2 ℃, through cleaning, drying, obtains the PtFe catalyst.Wherein PtFe average grain diameter 3.5nm, and dispersiveness better.
Embodiment 14
Get in the mixed solution of second alcohol and water that 7ml sulfonated polyether-ether-ketone (8wt%) joins 150ml, the mass ratio of second alcohol and water is 1: 1, adds 90wt% pyrroles's solution 10g again after stirring 5～10min, stirs 20～40min.The benzene sulfonic acid solution 20ml that with 0.6g potassium bichromate and concentration is 1mol/L again joins in the dispersion liquid, stirs 7 hours down at 0 ℃, after filtration, alcohol washes, and makes the composite polymer that is made of polypyrrole and sulfonated polyether-ether-ketone.It is distributed in the mixed solution of 200ml second alcohol and water, and the mass ratio of second alcohol and water is 2: 1, adds the H of 5g/L
2PtCl
6150ml, the PdCl of 5g/L
250ml, the MnCl of 5g/L
230ml regulates PH=10 with KOH, feeds He, adds hot reflux 50min at 95 ± 5 ℃, through cleaning, drying, obtains the PtPdMn catalyst.Wherein PtPdMn average grain diameter 4.6nm, and dispersiveness better.
Claims (4)
1. one kind is the fuel-cell catalyst of carrier with the composite polymer, it is characterized in that, described composite polymer is by conducting polymer and leads the proton polymer and constitute jointly.
2. composite polymer according to claim 1 is the fuel-cell catalyst of carrier, it is characterized in that, described conducting polymer is selected from polyaniline, polypyrrole or polythiophene.
3. composite polymer according to claim 1 is the fuel-cell catalyst of carrier, it is characterized in that the described proton polymer of leading is selected from perfluorinated sulfonic resin, SPSF resinoid, sulfonated polyphenyl sulfide resin, sulfonated polyphenyl and imidazoles, sulfonated polyimide resin, sulfonated polystyrene ion exchange resin or sulfonated polyether-ether-ketone resin.
4. the described composite polymer of claim 1 is the preparation method of the fuel-cell catalyst of carrier, it is characterized in that, prepare conducting polymer and the composite polymer of leading the proton polymer earlier, the metal supported catalyst particle is to the composite polymer surface then, and concrete preparation process is as follows:
Step 1: will lead the proton polymer dispersed in alcohol solution, and add the conducting polymer monomer then, and lead the mass ratio 0.1～100: 1 of proton polymer and conducting polymer monomer, and fully stir, and make dispersion liquid;
Step 2: the polymerization initiator of conducting polymer monomer is joined in the made dispersion liquid of step 1, maintain the temperature at 0～10 ℃, react and made monomer polymerization complete in 2～8 hours, make composite polymer;
Step 3: the composite polymer of step 2 preparation is scattered in the alcohol solution, add the metal precursor salting liquid, the mass ratio of conducting polymer monomer and metal catalyst particles is 0.1～100: 1, under N2, He or Ar protection, fully stir, 90～100 ℃ added hot reflux 30～60 minutes, made the fuel-cell catalyst that composite polymer is a carrier;
Alcohol is 0.5～100: 1 with the mass ratio of water in the wherein said alcohol solution, and alcohol is methyl alcohol, ethanol, propyl alcohol, ethylene glycol or isopropyl alcohol; Described conducting polymer is selected from polyaniline, polypyrrole or polythiophene; The described proton polymer of leading is selected from perfluorinated sulfonic resin, SPSF resinoid, sulfonated polyphenyl sulfide resin, sulfonated polyphenyl and imidazoles, sulfonated polyimide resin, sulfonated polystyrene ion exchange resin or sulfonated polyether-ether-ketone tree; Described polymerization initiator is made up of oxidant and Bronsted acid or is made of oxidant separately, wherein oxidant is Ammonium Persulfate 98.5, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ferric trichloride, dichromic acid amine or hydrogen peroxide, Bronsted acid comprises inorganic acid and organic acid two classes, inorganic acid is hydrochloric acid, nitric acid, sulfuric acid or perchloric acid, and organic acid is benzene sulfonic acid, DBSA or perfluorinated sulfonic resin; Metal is metal alloy or metal simple-substance in the described metallic catalyst, alloy is MxNy or MxNyOz, wherein x, y, z are each metal quality ratio in the catalyst, its numerical value is respectively the natural number in 0～100, and x+y=100 or x+y+z=100, M, N, O are respectively Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, W or Mo metallic element, and M, N, O are different, and metal simple-substance is Pt, Ru, Pd, Rh, Ir or Os.
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| CN102107147B (en) * | 2010-12-23 | 2012-07-18 | 西北师范大学 | Titanium dioxide and carbon composite material, preparation and application thereof |
| CN102107147A (en) * | 2010-12-23 | 2011-06-29 | 西北师范大学 | Titanium dioxide and carbon composite material, preparation and application thereof |
| CN103285919A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN103285919B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN103316706A (en) * | 2013-06-15 | 2013-09-25 | 湖南科技大学 | Metal-doped polyaniline and polypyrrole compound carbonization electric catalyst and preparation method thereof |
| CN103316706B (en) * | 2013-06-15 | 2015-03-11 | 湖南科技大学 | Metal-doped polyaniline and polypyrrole compound carbonization electric catalyst and preparation method thereof |
| CN112701297B (en) * | 2019-10-23 | 2023-02-28 | 中国科学院大连化学物理研究所 | High-stability non-noble metal catalyst electrode and preparation method and application thereof |
| CN112701297A (en) * | 2019-10-23 | 2021-04-23 | 中国科学院大连化学物理研究所 | High-stability non-noble metal catalyst electrode and preparation method and application thereof |
| CN112002915A (en) * | 2020-07-23 | 2020-11-27 | 北京卫星制造厂有限公司 | Oxygen electrode bifunctional catalyst, preparation method and application |
| CN113198538A (en) * | 2021-05-12 | 2021-08-03 | 江苏关山度新材料科技有限公司 | Preparation method of superstrong fiber-loaded Schiff base palladium catalyst |
| CN113198538B (en) * | 2021-05-12 | 2023-10-03 | 江苏关山度新材料科技有限公司 | Preparation method of super-strong fiber supported Schiff base palladium catalyst |
| CN114308065A (en) * | 2021-12-24 | 2022-04-12 | 苏州知益微球科技有限公司 | Monodisperse Fe30Mo1Preparation method of-Pt catalyst microspheres |
| CN114308065B (en) * | 2021-12-24 | 2024-03-08 | 苏州知益微球科技有限公司 | Monodisperse Fe 30 Mo 1 Preparation method of Pt catalyst microspheres |
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