CN102451727A - M/N-C catalyst and preparation and application thereof - Google Patents

M/N-C catalyst and preparation and application thereof Download PDF

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CN102451727A
CN102451727A CN2010105228232A CN201010522823A CN102451727A CN 102451727 A CN102451727 A CN 102451727A CN 2010105228232 A CN2010105228232 A CN 2010105228232A CN 201010522823 A CN201010522823 A CN 201010522823A CN 102451727 A CN102451727 A CN 102451727A
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ppy
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catalyst
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pyrrole monomer
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CN102451727B (en
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孙公权
齐静
姜鲁华
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Dalian Institute of Chemical Physics of CAS
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    • Y02E60/50—Fuel cells

Abstract

The invention relates to a non-platinum catalyst, in particular to an oxygen reduction catalyst for a proton exchange membrane fuel cell and preparation and application thereof. The catalyst can be prepared by the following steps of: (1) synthesizing polypyrrole (PPy); and (2) preparing an M/N-C catalyst, wherein the M/N-C catalyst can be taken as a cathode oxygen reduction catalyst for the proton exchange membrane fuel cell.

Description

A kind of M/N-C catalyst and preparation and application
Technical field
The present invention relates to non-platinum catalyst, relate to a kind of oxygen reduction catalyst and preparation and application that is used for Proton Exchange Membrane Fuel Cells specifically.
Background technology
Fuel cell has advantages such as energy conversion efficiency height, pollution-free, noiselessness, enjoys people's attention in recent years.Proton Exchange Membrane Fuel Cells is except the general characteristic with other fuel cells; But have advantages such as the high room temperature of specific power density and specific energy starts fast, no electrolyte loss, long service life simultaneously, have broad application prospects at aspects such as portable power source, dispersion power station, electric automobiles.
Catalyst is one of critical material of Proton Exchange Membrane Fuel Cells.At present, the catalyst of extensive use is to be the loaded or non-supported catalyst of main active component with the precious metals pt, but its Limited resources and higher cost to a great extent limit the development of Proton Exchange Membrane Fuel Cells.
In recent years, the researcher has carried out the research exploration to no-Pt catalyst.Has Metal-N 4The transition metal macrocyclic compound of structure is owing to it has preferably active to oxygen reduction reaction (ORR) and selectivity has caused researcher's very big interest.As far back as the sixties in 20th century, Jasinski etc. have reported to have Metal-N on Nature 4The transition metal macrocyclic compound of structure has catalytic activity to ORR.Yet, find that in research subsequently this type of transition metal macrocyclic compound is unstable in acid medium, can not practical application in fuel cell.The seventies in 20th century, the researcher finds, through the heat treatment under the inert atmosphere, can significantly improve its ORR activity and stable to transition metal macrocyclic compound.The macrocyclic compound of transition metal (comprising Cr, Fe, Mn, Ni, Co etc.); Like tetraphenylporphyrin (TPP), tetramethoxy phenyl porphyrin (TMPP), phthalocyanine chelates such as (Pc) as the eelctro-catalyst of low-temperature fuel cell by broad research, the result shows that the principal element that influences such eelctro-catalyst catalytic activity has the kind that contains nitrogen precursor in the kind, catalyst preparation process of central atom transition metal, heat treatment temperature etc.Still face a lot of problems at present but prepare catalyst with the transition metal macrocyclic compound high temperature pyrolysis, such as the preparation process more complicated of transition metal macrocycles such as porphyrin or phthalocyanines, commodity price is more high.The eighties in 20th century, Gupta etc. are N precursor preparation ORR catalyst with the macrocyclic compound of non-N4 structure first.The advantage of this method is that it can be a precursor with common inorganic salts, material with carbon element and the compound that contains N, has reduced the cost of catalyst.
At present, N precursor commonly used is NH 3, acetonitrile, pyrroles, the polymer that contains N and the carbon carrier of mixing N etc.Zelenay etc. are complex carrier with polypyrrole (PPy) and XC-72R; With the sodium borohydride is that reducing agent is prepared the Co-PPy composite catalyst (Co-PPy/C) on a kind of XC-72R of being carried on; With it is the hydrogen-air fuel cell test shows of negative electrode, and the eelctro-catalyst activity does not obviously reduce in 100 hours life experiment.Kunchan Lee etc. has compared the catalytic activity of heat treatment front and back Co-PPy/C composite catalysts, and the result shows that its catalytic activity is improved significantly after Overheating Treatment.Though it is PPy is a conducting polymer, relatively poor without the electric conductivity of doped P Py.In order to improve the electric conductivity of catalyst; The author with PPy and material with carbon element as complex carrier; But PPy and carbon carrier only are physical mixed, load on the carbon carrier Co can't with the PPy effect, can not form Co-N active sites structure; Cause the N complexing efficiency on Co and the PPy low, thereby reduced the catalytic activity of unit mass catalyst.
Summary of the invention
To the deficiency of prior art, the object of the invention is to provide a kind of novel non-platinum eelctro-catalyst and preparation and application that is applied to Proton Exchange Membrane Fuel Cells.
For realizing above-mentioned purpose, the present invention adopts following concrete scheme to realize:
A kind of M/N-C catalyst, the preparation method may further comprise the steps,
(1) polypyrrole (PPy) is synthetic:
A. in the water of surfactant or ethylene glycol solution, add pyrrole monomer, surfactant concentrations>=its critical micelle concentration wherein, the concentration of pyrrole monomer is 0.1-2molL -1, stirred 0.5-2 hour at 0-25 ℃, add oxidant afterwards, stir at 0-25 ℃ and made pyrrole monomer polymerization reaction take place generation polypyrrole (PPy) in 0.5-2 hour, the mol ratio of oxidant and pyrrole monomer is 0.5: 1-10: 1;
B. synthetic PPy is impregnated in the methanol aqueous solution that the quality percentage composition is 50-100%, to remove remaining surfactant and oxidant, filters afterwards, washing under 75 ℃ of vacuum conditions, was dried 3-6 hour;
(2) M/N-C Preparation of catalysts
A. the transition metal salt precursor being joined concentration is 1-2molL -1In the ethylene glycol solution of NaOH, the molar concentration of transition metal salt is 0.0001-0.05mol L -1, stirred 0.5-3 hour at 25-180 ℃ afterwards, add PPy afterwards, transition metal accounts for the 0.1-30% of transition metal and PPy quality total amount, continues to stir 0.5-3 hour, and the water that adds 10-40 times of volume afterwards carried out under 25-60 ℃ of stirring sedimentation 1-24 hour;
B. the mixture that step (2) a is obtained filters, and washing under the 30-75 ℃ of vacuum condition, was dried 3-6 hour;
C. with the sample after step (2) the b oven dry under noble gas atmosphere 500-900 ℃ heat treatment 1-3 hour, obtain target product M/N-C catalyst, M be among Fe, Co or the Ni one or more.
Said oxidant is (NH 4) 2S 2O 8Or H 2O 2Or Fe 3+, Cu 2+Salting liquid.
Said surfactant is one or more in eight alkyl trimethyl ammonium bromides (OTAB), ten alkyl trimethyl ammonium bromides (DeTAB), DTAB (DTAB), softex kw (CTAB), Sodium Polyacrylate (PAAS) or the polyvinylpyrrolidone (PVP).
In nitrate, sulfate, acetate, oxalates or the chloride that said transition metal salt precursor is iron, cobalt or nickel one or more.
The M/N-C catalyst of method for preparing, proton exchange film fuel cell cathodic oxygen reduction catalyst.
Compared with prior art; The present invention is under the prerequisite of not adding carbon carrier; Adopt cobalt salt and polypyrrole (PPy) direct impregnation; After making N effect on Co and the PPy form catalytic center, directly this sample of high-temperature heat treatment makes PPy that thermal decomposition take place and forms carbon skeleton, this carbon skeleton directly as the carbon carrier of new catalyst to strengthen the electric conductivity of catalyst.Simultaneously, Co and N are in the skeleton of carbon carrier, and the stability of catalyst will increase.This mode prepares the Co-PPy/C catalyst with traditional approach to be compared, and has reduced the Co that loads on the carbon carrier, makes that the N complexing efficiency on Co and the PPy improves, thereby has improved the catalytic activity of unit mass catalyst.In addition, it is simple that this catalyst also has the preparation process, and catalytic activity is high, and electric conductivity is strong, advantages such as good stability.
Description of drawings
Fig. 1 is the XRD spectra comparison of the sample for preparing according to embodiment 4 and comparative example 1 and 2;
Fig. 2 is according to embodiment 1,2, and 3 and 4 samples that prepare are at the saturated 0.5M HClO of oxygen 4ORR specific activity in the electrolyte;
Fig. 3 is that the sample for preparing according to embodiment 4 and comparative example 1,2,3 and 4 is at the saturated 0.5M HClO of oxygen 4ORR specific activity in the electrolyte;
The ORR specific activity that Fig. 4 is the sample for preparing according to embodiment 4 and comparative example 1,2,3 and 4 in the saturated 0.1M NaOH electrolyte of oxygen;
The ORR specific activity that Fig. 5 is the sample for preparing according to embodiment 7,8 and 9 in the saturated 0.1M NaOH electrolyte of oxygen;
The ORR specific activity before and after the stability test is in the saturated 0.1M NaOH electrolyte of oxygen for the sample for preparing according to embodiment 4 for Fig. 6.
The specific embodiment
Below in conjunction with embodiment the present invention is explained in detail.Certainly the present invention is not limited in these concrete embodiment.
Embodiment 1:
Be 0.8molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the electric alcohol solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 2molL -1In the ethylene glycol solution second of NaOH, the molar concentration of cobalt nitrate is 0.02mol L -1, stirred 3 hours at 180 ℃, add the PPy of aequum afterwards, cobalt accounts for 30% of cobalt and PPy quality total amount, continues to stir 2 hours, and the water that adds 40 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 6 hours;
With the 500 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 2:
Be 0.8molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 2molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt nitrate is 0.02molL -1, stirred 3 hours at 180 ℃ afterwards, add the PPy of aequum afterwards, cobalt accounts for 30% of cobalt and PPy quality total amount, continues to stir 2 hours, and the water that adds 40 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 50 ℃ of vacuum conditions, was dried 6 hours;
With the 700 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 3:
Be 0.8molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 20 ℃ of stirrings, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 2molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt nitrate is 0.02mol L -1, stirred 3 hours at 180 ℃ afterwards, add the PPy of aequum afterwards, cobalt accounts for 30% of cobalt and PPy quality total amount, continues to stir 2 hours, and the water that adds 40 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 6 hours;
With the 800 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 4:
Be 0.8molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 2molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt nitrate is 0.02molL -1, stirred 3 hours at 180 ℃ afterwards, add the PPy of aequum afterwards, cobalt accounts for 30% of cobalt and PPy quality total amount, continues to stir 2 hours, and the water that adds 40 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 30 ℃ of vacuum conditions, was dried 6 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 5:
Be 0.2molL at first in concentration -1The polyacrylic acid sodium water solution in add pyrrole monomer, the concentration of pyrrole monomer is 0.1molL -1, stirred 0.5 hour at 25 ℃, add oxidant (NH afterwards 4) 2S 2O 8, made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy), (NH in 2 hours 25 ℃ of stirrings 4) 2S 2O 8With the mol ratio of pyrrole monomer be 8: 1;
It is in 60% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt acetate ((CH 3CO 2) 2Co) joining concentration is 1.5molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt acetate is 0.05mol L -1, stirred 3 hours at 160 ℃ afterwards, add the PPy of aequum afterwards, cobalt accounts for 18% of cobalt and PPy quality total amount, continues to stir 1 hour, and the water that adds 10 times of volumes afterwards carried out sedimentation 24 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 5 hours;
With the 900 ℃ of heat treatment 1 hour under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 6:
Be 1molL at first in concentration -1DTAB (DTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 2molL -1, stirred 2 hours at 25 ℃, add oxidant ferric nitrate (Fe (NO afterwards 3) 36H 2O), 25 ℃ of stirrings the pyrrole monomer polymerization reaction take place is generated and gather pyrrole (PPy), the mol ratio of ferric nitrate and pyrrole monomer is 2: 1;
It is in 80% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt oxalate (CoC 2O 42H 2O) joining concentration is 1molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt oxalate is 0.001mol L -1, stirred 3 hours at 25 ℃, add the PPy of aequum afterwards, cobalt accounts for 5% of cobalt and PPy quality total amount, continues to stir 3 hours, and the water that adds 30 times of volumes afterwards carried out sedimentation 24 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 6 hours;
With the 900 ℃ of heat treatment 2 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 7:
Be 1molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 1molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt nitrate is 0.005mol L -1, stirred 3 hours at 120 ℃, add the PPy of aequum afterwards, cobalt accounts for 5% of cobalt and PPy quality total amount, continues to stir 1 hour, and the water that adds 20 times of volumes afterwards carried out sedimentation 10 hours under 40 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 5 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Embodiment 8:
Be 1molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With ferric acetate ((CH 3CO 2) 3Fe) joining concentration is 1molL -1In the ethylene glycol solution of NaOH, the molar concentration of ferric acetate is 0.005mol L -1, stirred 3 hours at 140 ℃, add the PPy of aequum afterwards, iron accounts for 5% of iron and PPy quality total amount, continues to stir 1 hour, and the water that adds 30 times of volumes afterwards carried out sedimentation 24 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target and produce the Fe/N-C catalyst.
Embodiment 9:
Be 1molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With nickelous sulfate (Ni 2SO 4) to join concentration be 1molL -1In the ethylene glycol solution of NaOH, the molar concentration of nickelous sulfate is 0.005mol L -1, stirred 3 hours at 100 ℃, add the PPy of aequum afterwards, nickel accounts for 5% of nickel and PPy quality total amount, continues to stir 1 hour, and the water that adds 10 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 5 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Ni/N-C catalyst.
Embodiment 10:
Be 0.3molL at first in concentration -1The polyvinylpyrrolidone aqueous solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 2 hours at 25 ℃, add oxidants hydrogen peroxide (H afterwards 2O 2), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 25 ℃ of stirrings, the mol ratio of hydrogen peroxide and pyrrole monomer is 10: 1;
It is in 50% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With cobalt chloride (CoCl 26H 2O) joining concentration is 1molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt chloride is 0.001mol L -1, stirred 0.5 hour at 25 ℃, add the PPy of aequum afterwards, cobalt accounts for 0.1% of cobalt and PPy quality total amount, continues to stir 0.5 hour, and the water that adds 10 times of volumes afterwards carried out sedimentation 24 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/N-C catalyst.
Comparative example 1:
Be 0.8molL at first in concentration -1Softex kw (CTAB) ethylene glycol solution in add pyrrole monomer, the concentration of pyrrole monomer is 1molL -1, stirred 1 hour at 0 ℃, add oxidant ferric trichloride (FeCl afterwards 3), made the pyrrole monomer polymerization reaction take place generate polypyrrole (PPy) in 2 hours 0 ℃ of stirring, the mol ratio of ferric trichloride and pyrrole monomer is 0.5: 1;
It is in 100% the methanol aqueous solution that the PPy that is synthesized is impregnated into the quality percentage composition, to remove remaining surfactant and oxidant, filters afterwards, and washing under 75 ℃ of vacuum conditions, was dried 3 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product N-C catalyst.
Comparative example 2:
With cobalt nitrate (Co (NO 3) 26H 2O) joining concentration is 2molL -1In the ethylene glycol solution of NaOH, the molar concentration of cobalt nitrate is 0.02mol L -1, stirring 3 hours at 180 ℃, the carbon carrier Vulcan XC-72R that adds aequum afterwards (is labeled as XC; Cabot company); Cobalt accounts for 30% of cobalt and XC quality total amount, continues to stir 1 hour, and the water that adds 40 times of volumes afterwards carried out sedimentation 12 hours under 60 ℃ of stirrings;
The mixture that obtains is filtered, and washing under 40 ℃ of vacuum conditions, was dried 6 hours;
With the 900 ℃ of heat treatment 3 hours under high pure nitrogen atmosphere of the sample after the oven dry, obtain target product Co/XC catalyst.
Comparative example 3:
With commodity 40wt.%Pt/C catalyst (Johnson Matthey company) as a comparison.
Comparative example 4:
With commodity carbon carrier Vulcan XC-72R (being labeled as XC, Cabot company) as a comparison.
Fig. 1 is the XRD spectra comparison of the sample for preparing according to embodiment 4 and comparative example 1 and 2.Can find out that the N-C catalyst that is prepared by comparative example 1 demonstrates the architectural feature of material with carbon element, near its diffraction maximum that is positioned at 25 ° belongs to graphite (002) diffraction maximum.The Co/XC catalyst that Co/N-C catalyst that is prepared by embodiment 4 and comparative example 2 prepare all shows face-centered cubic (fcc) structure of metal Co, and average grain diameter is respectively 18.4 and 21.1nm.
Fig. 2 is according to embodiment 1,2, and 3 and 4 samples that prepare are at the saturated 0.5M HClO of oxygen 4ORR specific activity in the electrolyte.The electrode rotating speed is 1600rpm, and sweep speed is 10mV/s.Can find out that from figure along with the raising of heat treatment temperature, activity of such catalysts also increases accordingly.
Fig. 3 is that the sample for preparing according to embodiment 4 and comparative example 1,2,3 and 4 is at the saturated 0.5M HClO of oxygen 4ORR specific activity in the electrolyte.The electrode rotating speed is 1600rpm, and sweep speed is 10mV/s.Can know that from Fig. 3 the active order of ORR is XC＜N-C＜Co/XC＜Co/N-C＜Pt/C.The result shows that it is active that the material with carbon element of the N that mixed has ORR; Simultaneously, compare with N-C, the adding of Co has obviously improved the ORR activity of Co/N-C catalyst; Though also have certain gap with commodity Pt/C activity of such catalysts, to compare with the Co/XC catalyst that similar preparation method obtains, the Co/N-C catalyst has remarkable advantages.
The ORR specific activity that Fig. 4 is the sample for preparing according to embodiment 4 and comparative example 1,2,3 and 4 in the saturated 0.1M NaOH electrolyte of oxygen.The electrode rotating speed is 1600rpm, and sweep speed is 10mV/s.Can know that from Fig. 4 the active order of ORR is XC＜Co/XC＜N-C＜Co/N-C＜Pt/C.The result shows; The initial hydrogen reduction current potential of the ORR of Co/N-C catalyst is than the low 100-150mV of commodity Pt/C; Though also have certain gap with commodity Pt/C activity of such catalysts; But the ORR activity of Co/N-C catalyst obviously is superior to Co/XC, and its initial hydrogen reduction current potential is than Co/XC about 80mV that shuffles, and its half wave potential is than Co/XC about 140mV that shuffles.
The ORR specific activity that Fig. 5 is the sample for preparing according to embodiment 7,8 and 9 in the saturated 0.1M NaOH electrolyte of oxygen.The electrode rotating speed is 1600rpm, and sweep speed is 10mV/s.As shown in Figure 5, be that the ORR activity of Co/N-C catalyst of metal center is active greater than the ORR of Fe/N-C and Ni/N-C catalyst that is metal center with Co with Fe and Ni.
The ORR specific activity before and after the stability test is in the saturated 0.1M NaOH electrolyte of oxygen for the sample for preparing according to embodiment 4 for Fig. 6.The electrode rotating speed is 1600rpm, and sweep speed is 10mV/s.Can find out, through (100mV s behind the cyclic voltammetry scan of 1000 circles -1,-0.8～0.3Vvs.Hg/HgO), activity of such catalysts is not decay almost, explains that the Co/N-C catalyst has stability preferably under test condition.

Claims (10)

1. M/N-C catalyst, it is characterized in that: it can prepare as follows,
(1) polypyrrole (PPy) is synthetic:
A. in the water of surfactant and/or ethylene glycol solution, add pyrrole monomer, surfactant concentrations>=its critical micelle concentration wherein, the concentration of pyrrole monomer is 0.1-2molL -1, stirred 0.5-2 hour at 0-25 ℃; Add oxidant afterwards, stir at 0-25 ℃ and made pyrrole monomer polymerization reaction take place generation polypyrrole (PPy) in 0.5-2 hour, the mol ratio of oxidant and pyrrole monomer is 0.5: 1-10: 1;
B. synthetic PPy is impregnated in the methanol aqueous solution that the quality percentage composition is 50-100%,, filters washing, drying afterwards to remove remaining surfactant and oxidant;
(2) M/N-C Preparation of catalysts
A. one or more salt precursor among transition-metal Fe, Co or the Ni being joined concentration is 1-2molL -1In the ethylene glycol solution of NaOH, the molar concentration of transition metal salt is 0.0001-0.05mol L -1, stirred 0.5-3 hour at 25-180 ℃ afterwards, add PPy afterwards, transition metal accounts for the 0.1-30% of transition metal and PPy quality total amount, continues to stir 0.5-3 hour, and the water that adds 10-40 times of volume afterwards carried out under 25-60 ℃ of stirring sedimentation 1-24 hour;
B. the mixture that step (2) a is obtained filters, washing, drying;
C. with the sample after step (2) the b oven dry under noble gas atmosphere 500-900 ℃ heat treatment 1-3 hour, obtain target product M/N-C catalyst, M be among Fe, Co or the Ni one or more.
2. M/N-C catalyst according to claim 1, it is characterized in that: step (1) b and step (2) b drying condition are under the 30-75 ℃ of vacuum condition, dry 3-6 hour.
3. M/N-C catalyst according to claim 1, it is characterized in that: said oxidant is (NH 4) 2S 2O 8Or H 2O 2Or Fe 3+, Cu 2+Soluble-salt solution.
4. M/N-C catalyst according to claim 1, it is characterized in that: said surfactant is one or more in eight alkyl trimethyl ammonium bromides (OTAB), ten alkyl trimethyl ammonium bromides (DeTAB), DTAB (DTAB), softex kw (CTAB), Sodium Polyacrylate (PAAS) or the polyvinylpyrrolidone (PVP).
5. M/N-C Preparation of catalysts method, it is characterized in that: it can prepare as follows,
(1) polypyrrole (PPy) is synthetic:
A. in the water of surfactant and/or ethylene glycol solution, add pyrrole monomer, surfactant concentrations>=its critical micelle concentration wherein, the concentration of pyrrole monomer is 0.1-2molL -1, stirred 0.5-2 hour at 0-25 ℃; Add oxidant afterwards, stir at 0-25 ℃ and made pyrrole monomer polymerization reaction take place generation polypyrrole (PPy) in 0.5-2 hour, the mol ratio of oxidant and pyrrole monomer is 0.5: 1-10: 1;
B. synthetic PPy is impregnated in the methanol aqueous solution that the quality percentage composition is 50-100%,, filters washing, drying afterwards to remove remaining surfactant and oxidant;
(2) M/N-C Preparation of catalysts
A. one or more salt precursor among transition-metal Fe, Co or the Ni being joined concentration is 1-2molL -1In the ethylene glycol solution of NaOH, the molar concentration of transition metal salt is 0.0001-0.05mol L -1, stirred 0.5-3 hour at 25-180 ℃ afterwards, add PPy afterwards, transition metal accounts for the 0.1-30% of transition metal and PPy quality total amount, continues to stir 0.5-3 hour, and the water that adds 10-40 times of volume afterwards carried out under 25-60 ℃ of stirring sedimentation 1-24 hour;
B. the mixture that step (2) a is obtained filters, washing, drying;
C. with the sample after step (2) the b oven dry under noble gas atmosphere 500-900 ℃ heat treatment 1-3 hour, obtain target product M/N-C catalyst, M be among Fe, Co or the Ni one or more.
6. like the said M/N-C Preparation of catalysts of claim 5 method, it is characterized in that: step (1) b and step (2) b drying condition are under the 30-75 ℃ of vacuum condition, dry 3-6 hour.
7. like the said M/N-C Preparation of catalysts of claim 5 method, it is characterized in that: said oxidant is (NH 4) 2S 2O 8Or H 2O 2Or Fe 3+, Cu 2+Soluble-salt solution.
8. like the said M/N-C Preparation of catalysts of claim 5 method, it is characterized in that: said surfactant is one or more in eight alkyl trimethyl ammonium bromides (OTAB), ten alkyl trimethyl ammonium bromides (DeTAB), DTAB (DTAB), softex kw (CTAB), Sodium Polyacrylate (PAAS) or the polyvinylpyrrolidone (PVP).
9. like the said M/N-C Preparation of catalysts of claim 5 method, it is characterized in that: one or more in nitrate, sulfate, acetate, oxalates or the chloride that said transition metal salt precursor is iron, cobalt or nickel.
10. the described M/N-C catalyst of claim 1 proton exchange film fuel cell cathodic oxygen reduction catalyst.
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