CN102806106A - Preparation method of carbon-supported metal polypyrrole oxygen reduction catalyst - Google Patents
Preparation method of carbon-supported metal polypyrrole oxygen reduction catalyst Download PDFInfo
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- CN102806106A CN102806106A CN2012102893825A CN201210289382A CN102806106A CN 102806106 A CN102806106 A CN 102806106A CN 2012102893825 A CN2012102893825 A CN 2012102893825A CN 201210289382 A CN201210289382 A CN 201210289382A CN 102806106 A CN102806106 A CN 102806106A
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Abstract
The invention relates to a preparation method of a carbon-supported metal polypyrrole oxygen reduction catalyst. The method comprises the following steps of dissolving a certain quantity of metal precursors into a solvent; and then adding a carbon material to the solvent; uniformly dispersing the carbon material in the solvent; adding pyrrole to the solvent; after sufficiently stirring the solvent, adding an oxidizing agent to the solvent; and then carrying out polymerization reaction on a mixture during stirring; transferring an obtained product to an inert atmosphere shielded high temperature environment after the product is dried; and carrying out heat treatment on the product so as to obtain a target catalyst. Compared with the prior art, the preparation method for the carbon-supported metal polypyrrole oxygen reduction catalyst, provided by the invention, has the advantages of simple process, short time, low cost, high performance and so on.
Description
Technical field
The invention belongs to the catalyst research of fuel cell field, be specifically related to the preparation method of a kind of fuel cell with carbon-supported metal polypyrrole class oxygen reduction catalyst.
Background technology
Along with constantly highlighting of the energy and environmental problem, the exploitation of the clean and effective energy receives increasing concern.Fuel cell power generation is the generation technology of new generation after waterpower, firepower and nuclear energy power generation, and it is a kind of efficient generating apparatus that directly through the mode of electrochemical reaction the chemical energy of fuel and oxidant is changed into electric energy without burning.Because of the basic principle of this device is that the galvanic cell reaction does not relate to burning, its energy conversion efficiency does not receive the restriction of " Carnot cycle ", and theoretical efficiency can reach more than 90%, actual service efficiency then be ordinary internal combustion engine 2-3 doubly.Numerous advantages such as in addition, it also has the fuel variation, noise is low, environmental pollution is little, good reliability.Therefore, the development of fuel cell is not merely the solution environmental problem new thinking is provided, and for solving serious day by day problem of energy crisis new approach is provided.Proton Exchange Membrane Fuel Cells (PEMFC) is except the general characteristic with above-mentioned fuel cell; Also have and start fast, specific power and the high outstanding advantage of specific energy; Become the focus of current fuel cell field research, its technological development and application progress is very fast.At present, cost height and life-span weak point are two big outstanding problems of restriction PEMFC development, and one of key factor that causes this two large problems is its electrode catalyst, especially the cathodic oxygen reduction catalyst.At present, the oxygen electrode catalyst of business-like PEMFC adopts carbon to carry noble metal catalysts such as platinum or platinum alloy more, and such catalyst also is the best oxygen reduction catalyst of effect of generally acknowledging at present.But noble metal platinum is very low at natural reserves, and costs an arm and a leg, thereby to cause with it be that the PEMFC cost of oxygen electrode catalyst is too high, has hindered popularizing and promoting of PEMFC greatly.Therefore, the exploitation of non noble metal oxygen reduction catalyst has become the research emphasis in PEMFC field, and it is successfully developed is the only way which must be passed of PEMFC large-scale commercial applications application.
In recent years, along with about the electric conductivity of polypyrrole (PPy) and going deep into of THERMAL STABILITY, its application in the PEMFC oxygen electrode catalyst has caused various countries researchers' extensive concern.Method through the electrochemical polymerization pyrroles such as Yuasa is after carbon material surface coats PPy; It is dispersed in the methanol solution of cobalt acetate with at the surface adsorption cobalt ions; After the vacuum environment high-temperature heat treatment, obtain having Co-PPy/C catalyst (the Chemistry of Materials 2005 of hydrogen reduction catalytic activity then; 17,4278-4281).Bashyam etc. are that the method that oxidant passes through chemical polymerization has prepared the material with carbon element of PPy finishing with the hydrogen peroxide solution, and it is at Co (NO
3)
26H
2Abundant dispersion and adsorption of cobalt ion are after NaBH in the aqueous solution of O
4CATALYST Co-PPy/C that reduction makes not only shows high hydrogen reduction catalytic activity, and has good stable property.With it is the H of cathod catalyst
2-O
2Proton Exchange Membrane Fuel Cells is that 80 ℃, both positive and negative polarity all adopt under the condition of 2atm back pressure in operating temperature, and maximum power density reaches 0.14W/cm
2, and 100 hours performances of continuous operation are unattenuated, and (Nature 443,2006,63-66).The method of employing Bashyam such as Lee etc. is added the oxygen reduction catalyst Co-PPy/C that follow-up blanket of nitrogen high-temperature heat treatment has prepared superior performance; And point out that high-temperature heat treatment has very important facilitation (Electrochimica Acta 2009 to the Co-PPy/C class oxygen reduction catalyst that makes excellent performance; 54,4704-4711).On the basis of these work; In order further to improve the performance of carbon-supported metal polypyrrole class oxygen reduction catalyst; Yuan etc. with ammonium persulfate (APS) method that is oxidant through chemical polymerization after carbon material surface coats PPy; It is dispersed in the aqueous solution of cobalt acetate with at the surface adsorption cobalt ions, and the performance of the Co-PPy/C catalyst that high-temperature heat treatment makes under blanket of nitrogen then improves significantly than results reported in the past, is the H of cathod catalyst with it
2-O
2Proton Exchange Membrane Fuel Cells is that 80 ℃, both positive and negative polarity all do not have under the temperate condition of back pressure in operating temperature, and maximum power density reaches 0.16W/cm
2If in the polymerization process of PPy, add p-methyl benzenesulfonic acid (TsOH) as adulterant, the performance of the CATALYST Co-PPy-TsOH/C that makes can further improve, and is the H of cathod catalyst with it
2-O
2Proton Exchange Membrane Fuel Cells maximum power density under the same conditions reaches 203mW/cm
2, when applying the back pressure of 1atm, reach 250mW/cm
2More than (Journal of the American Chemical Society 2010,132 (6): 1754-1755).This method is the best approach of the preparation high-performance Co-PPy/C class oxygen reduction catalyst reported in the world up to now.This method of employings such as Wu prepared the Fe-PPy/C catalyst (ECS Transactions 2009,25,1299-1311).They are oxidant, FeCl with APS
3Be metal precursor, coat PPy, FeCl through carbon material surface
3Though the Fe-PPy/C catalyst that processes such as the absorption of the iron ion in the solution, blanket of nitrogen high-temperature heat treatment make shows initial performance preferably, stable extreme difference in PEMFC.
In a word,, but still exist the preparation process loaded down with trivial details, complicated, thereby be unfavorable for problems such as large-scale production and the further raising of hydrogen reduction catalytic performance needs though the development of carbon-supported metal polypyrrole class oxygen reduction catalyst has obtained significant progress.
Summary of the invention
The object of the invention is exactly the preparation method that the carbon-supported metal polypyrrole class oxygen reduction catalyst that a kind of process is simple, the time is short, cost is low, performance is high is provided for the defective that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme: a kind of preparation method of carbon-supported metal polypyrrole class oxygen reduction catalyst; It is characterized in that; This method may further comprise the steps: a certain amount of metal precursor is dissolved in the solvent, adds material with carbon element then and evenly disperse therein, add the pyrroles again; Fully stir the back and add oxidant, polymerisation 0.1-8h under stirring condition then; Be transferred to after the products therefrom drying that heat treatment 0.1-10h promptly makes the target catalyst in the hot environment of inert atmosphere protection; The pyrroles who uses in the catalyst preparation process and the mol ratio of oxidant are 20: 1-1: 15; Ratio between the milliliter number of pyrroles's mM number and solvent is 1: 15-1: 120; Gross mass in pyrroles, metal precursor and material with carbon element is 100%; Pyrroles's quality is 5-30%, and the quality of contained metal is 0.02-13% in the metal precursor, and the quality of material with carbon element is 20-99.9%.
Contained metal is cobalt or iron in the described metal precursor.
Described metal precursor is oxalates, acetate, nitrate, sulfate or the chloride of metal.
Described solvent is water, isopropyl alcohol, ethanol, ethylene glycol or pyridine.
Described material with carbon element is carbon black, carbon fiber, CNT, charcoal-aero gel, active carbon, Graphene or its mixture.
Described oxidant is ammonium persulfate, hydrogen peroxide solution or trivalent iron salt.
Also can add adulterant when adding oxidant, the addition of adulterant is: the mol ratio of pyrroles and adulterant is 1: 1-25: 1.
Described adulterant is benzene sulfonic acid, p-methyl benzenesulfonic acid, DBSA, naphthalene sulfonic acids and salt thereof and derivative.
Described inert gas is nitrogen or argon gas.
Heat treated temperature is 300-1200 ℃ in the described hot environment.
The present invention is directed to loaded down with trivial details, the complex process of carbon-supported metal polypyrrole class oxygen reduction catalyst building-up process, and the problem that further improves of performance need, provide a kind of not only simple but also can effectively improve the novel preparation method of catalyst performance.The present invention has not only simplified the Preparation of catalysts process, has shortened the Preparation of catalysts time, has reduced the Preparation of catalysts cost, and the hydrogen reduction catalytic performance of the catalyst that makes also is significantly improved than the catalyst of conventional method preparation.Compare with the best approach of the preparation high-performance carbon-supported metal polypyrrole class oxygen reduction catalyst of present report (three-step synthesis method: 1. carbon surface PPy coating decoration, 2. metal ion surface adsorption, 3. high-temperature heat treatment); The preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst unites two into one carbon surface PPy coating decoration and two steps of metal ion surface adsorption; Not only simplify the Preparation of catalysts process, shortened the Preparation of catalysts time, reduced the Preparation of catalysts cost; And the electrochemical property test result shows, the performance of the catalyst that obviously is superior to by the hydrogen reduction catalytic performance of the catalyst of this inventive method preparation being made by the existing best approach.
Therefore, the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst helps promoting the real application of carbon-supported metal polypyrrole class oxygen reduction catalyst in fuel cell.
Description of drawings
Fig. 1 adopts the H of the carbon-supported metal polypyrrole class oxygen reduction catalyst of the inventive method and the best approach preparation of report at present at the saturated 0-5mol/L of oxygen respectively
2SO
4Hydrogen reduction catalytic performance cyclic voltammetry curve contrast in the solution.
Wherein, curve a is the cyclic voltammetry curve by the CATALYST Co-PPy-TsOH-APS/BP2000-new of embodiment 1 preparation; Curve b is the cyclic voltammetry curve by the CATALYST Co-PPy-TsOH-APS/BP2000-old of comparative example 1 preparation.
The specific embodiment
The method of testing of the catalyst performance that the present invention uses is following:
The Nafion emulsion (Aldrich) of 5wt% of getting catalyst and the 0.05ml of 5mg places centrifuge tube; Add distilled water and be mixed with the mixed liquor of 1ml through ultrasonic dispersion; Use microsyringe to get 10 μ l mixing drops then in the glass-carbon electrode surface of diameter as 4mm; As working electrode, and be that reference electrode, diameter are that the platinum filament of 1mm is the H of auxiliary electrode, 0.5mol/L after the room temperature air dried with saturated calomel electrode (SCE)
2SO
4Solution is that electrolyte is formed three-electrode system, in the potential range of-0.2-0.8V (with respect to saturated calomel electrode SCE) with the potential scanning speed test loop volt-ampere curve of 5mV/s.Before test is carried out, the H of 0.5mol/L
2SO
4Solution is earlier saturated with oxygen.
Comprise that at institute of the present invention drawings attached in the specification digest drawing and description accompanying drawing, all potential values all have been scaled the current potential with respect to standard hydrogen electrode (NHE).
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1:
Take by weighing 0.2g four hydration cobalt acetates and it is dissolved in the isopropyl alcohol of 100ml; Fully stir the back and add 0.6gBlack Pears 2000 (BP2000) carbon black; The pyrroles who adds 3mmol behind the ultrasonic dispersion 30min; Ammonium persulfate (APS) solution and the p-methyl benzenesulfonic acid (TsOH) of 0.19g, the polymerisation 4h under the magnetic agitation then that add the 0.06mol/L of 100ml behind the stirring 30min.Products therefrom is transferred in the round-bottomed flask and passes through the rotary evaporation solvent evaporated down in water bath with thermostatic control; Be transferred to product in the quartz boat then and place the tube furnace of nitrogen protection; Keep 2h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-TsOH-APS/BP2000-new.
Curve a is CATALYST Co-PPy-TsOH-APS/BP2000-new of being made by embodiment 1 H at the saturated 0.5mol/L of oxygen in the accompanying drawing 1
2SO
4The cyclic voltammetry curve of the hydrogen reduction catalytic performance in the solution.Wherein hydrogen reduction spike potential and peak current are respectively 0.731V and 0.276mA, apparently higher than spike potential 0.710V and the peak current 0.174mA (seeing the curve b in the accompanying drawing 1) of the CATALYST Co-PPy-TsOH-APS/BP2000-old that is made by comparative example 1.The CATALYST Co that explanation is made by the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst-PPy-TsOH-APS/BP2000-new has better hydrogen reduction catalytic performance than CATALYST Co-PPy-TsOH-APS/BP2000-old that the best approach by present report makes.
Embodiment 2:
Take by weighing the 0.5g cabaltous nitrate hexahydrate and it is dissolved in the isopropyl alcohol of 100ml adding 0.8g Graphene (Graphene) after the abundant stirring, the pyrroles of adding 2mmol behind the ultrasonic dispersion 30min, the ferric trichloride (FeCl of the 0.1mol/L of adding 90ml behind the stirring 30min
3) DBSA (ABS) of solution and 0.22g, polymerisation 3h under the magnetic agitation then.Products therefrom is transferred in the round-bottomed flask and passes through the rotary evaporation solvent evaporated down in water bath with thermostatic control; Be transferred to product in the quartz boat then and place the tube furnace of nitrogen protection; Keep 3h after rising to 900 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-ABS-FeCl
3/ Graphene-new.
H at the saturated 0.5mol/L of oxygen
2SO
4Hydrogen reduction catalytic performance cyclic voltammetric test result in the solution shows, the CATALYST Co-PPy-ABS-FeCl that is made by embodiment 2
3The spike potential of/Graphene-new and peak current are all apparently higher than the CATALYST Co-PPy-ABS-FeCl that is made by comparative example 2
3/ Graphene-old.CATALYST Co-PPy-ABS-FeCl that explanation is made by the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst
3CATALYST Co-PPy-ABS-FeCl that/Graphene-new makes than the best approach by present report
3/ Graphene-old has better hydrogen reduction catalytic performance.
Embodiment 3:
Take by weighing the 0.4g Diaquaoxalato cobalt and it is dissolved in the isopropyl alcohol of 100ml abundant stirring back adding 0.6gVulcan XC-72 carbon black, the pyrroles of adding 3mmol behind the ultrasonic dispersion 30min, the hydrogen peroxide solution (H of the 30wt% of adding 1ml behind the stirring 30min
2O
2) solution, polymerisation 2h under the magnetic agitation then.Products therefrom is transferred in the round-bottomed flask and passes through the rotary evaporation solvent evaporated down in water bath with thermostatic control; Be transferred to product in the quartz boat then and place the tube furnace of nitrogen protection; Keep 1.5h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-H
2O
2/ XC72-new.
H at the saturated 0.5mol/L of oxygen
2SO
4Hydrogen reduction catalytic performance cyclic voltammetric test result in the solution shows, the CATALYST Co-PPy-H that is made by embodiment 3
2O
2The spike potential of/XC72-new and peak current are all apparently higher than the CATALYST Co-PPy-H that is made by comparative example 3
2O
2/ xC72-old.CATALYST Co-PPy-H that explanation is made by the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst
2O
2CATALYST Co-PPy-H that/XC72-new makes than the best approach by present report
2O
2/ XC72-old has better hydrogen reduction catalytic performance.
Embodiment 4;
Take by weighing 0.32g nine nitric hydrate iron and it is dissolved in the isopropyl alcohol of 100ml; Fully stir the back and add 0.6g Black Pears 2000 (BP2000) carbon black; The pyrroles who adds 3mmol behind the ultrasonic dispersion 30min; Ammonium persulfate (APS) solution and the p-methyl benzenesulfonic acid (TsOH) of 0.19g, the polymerisation 4h under the magnetic agitation then that add the 0.06mol/L of 100ml behind the stirring 30min.Products therefrom is transferred in the round-bottomed flask and passes through the rotary evaporation solvent evaporated down in water bath with thermostatic control; Be transferred to product in the quartz boat then and place the tube furnace of nitrogen protection; Keep 2h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get catalyst Fe-PPy-TsOH-APS/BP2000-new.
H at the saturated 0.5mol/L of oxygen
2SO
4Hydrogen reduction catalytic performance cyclic voltammetric test result in the solution shows, the spike potential of the catalyst Fe-PPy-TsOH-APS/BP2000-new that is made by embodiment 4 and peak current are all apparently higher than the catalyst Fe-PPy-TsOH-APS/BP2000-old that is made by comparative example 4.The catalyst Fe that explanation is made by the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst-PPy-TsOH-APS/BP2000-new has better hydrogen reduction catalytic performance than catalyst Fe-PPy-TsOH-APS/BP2000-old that the best approach by present report makes.
Embodiment 5:
Take by weighing 0.56g five oxalic acid hydrate iron and it is dissolved in the 100ml isopropyl alcohol abundant stirring back adding 0.8gVulcan XC-72 carbon black, the pyrroles of adding 5mmol behind the ultrasonic dispersion 30min, the hydrogen peroxide solution (H of the 30wt% of adding 1ml behind the stirring 30min
2O
2) solution, polymerisation 5h under the magnetic agitation then.Products therefrom is transferred in the round-bottomed flask and passes through the rotary evaporation solvent evaporated down in water bath with thermostatic control; Be transferred to product in the quartz boat then and place the tube furnace of nitrogen protection; Keep 3h after rising to 900 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get catalyst Fe-PPy-H
2O
2/ XC72-new.
H at the saturated 0.5mol/L of oxygen
2SO
4Hydrogen reduction catalytic performance cyclic voltammetric test result in the solution shows, the catalyst Fe-PPy-H that is made by embodiment 5
2O
2The spike potential of/XC72-new and peak current are all apparently higher than the catalyst Fe-PPy-H that is made by comparative example 5
2O
2/ XC72-old.Catalyst Fe-PPy-H that explanation is made by the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst
2O
2Catalyst Fe-PPy-H that/XC72-new makes than the best approach by present report
2O
2/ xC72-old has better hydrogen reduction catalytic performance.
Comparative example 1:
Take by weighing 0.6g Black Pears 2000 (BP2000) carbon black; Join in the conical flask that the 100ml isopropyl alcohol is housed; Add the pyrroles of 3mmol and the distilled water of 100ml behind the ultrasonic dispersion 30min; Ammonium persulfate (APS) solution and the p-methyl benzenesulfonic acid (TsOH) of 0.19g, the polymerisation 4h under the magnetic agitation then that add the 0.06mol/L of 100ml behind the stirring 30min.Products therefrom filters the back with absolute ethyl alcohol and distilled water cyclic washing; 45 ℃ of dry 12h obtain the material with carbon element of surperficial PPy coating decoration then; Itself and 0.2g four hydration cobalt acetates are joined in the conical flask that the 200ml distilled water is housed; Stir 2h behind the ultrasonic dispersion 1h, be transferred to subsequently in the round-bottomed flask, pass through the rotary evaporation solvent evaporated down in water bath with thermostatic control.Be transferred to products therefrom in the quartz boat then and place the tube furnace of nitrogen protection, keep 2h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-TsOH-APS/BP2000-old.
Curve b is CATALYST Co-PPy-TsOH-APS/BP2000-old of being made by comparative example 1 H at the saturated 0.5mol/L of oxygen in the accompanying drawing 1
2SO
4The cyclic voltammetry curve of the hydrogen reduction catalytic performance in the solution.Wherein hydrogen reduction spike potential and peak current are respectively 0.710V and 0.174mA, be starkly lower than the CATALYST Co-PPy-TsOH-APS/BP2000-new that makes by embodiment 1 spike potential 0.731V and peak current 0.276mA (see in the accompanying drawing 1 curve a).The performance of CATALYST Co-PPy-TsOH-APS/BP2000-new that the hydrogen reduction catalytic performance of CATALYST Co-PPy-TsOH-APS/BP2000-old that explanation is made by the best approach of present report obviously makes than the preparation method of a kind of carbon-supported metal polypyrrole of the present invention class oxygen reduction catalyst is poorer.
Comparative example 2:
Take by weighing 0.8g Graphene (Graphene), join in the conical flask that the 100ml isopropyl alcohol is housed, add the pyrroles of 2mmol and the distilled water of 100ml behind the ultrasonic dispersion 30min, add the ferric trichloride (FeCl of the 0.1mol/L of 90ml behind the stirring 30min
3) DBSA (ABS) of solution and 0.22g, polymerisation 3h under the magnetic agitation then.Products therefrom filters the back with absolute ethyl alcohol and distilled water cyclic washing; 50 ℃ of dry 10h obtain the grapheme material of surperficial PPy coating decoration then; Itself and 0.5g cabaltous nitrate hexahydrate are joined in the conical flask that the 200ml distilled water is housed; Stir 2h behind the ultrasonic dispersion 1.5h, be transferred to subsequently in the round-bottomed flask, pass through the rotary evaporation solvent evaporated down in water bath with thermostatic control.Be transferred to products therefrom in the quartz boat then and place the tube furnace of nitrogen protection, keep 3h after rising to 900 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-ABS-FeCl
3/ Graphene-old.
Comparative example 3:
Take by weighing 0.6g Vulcan XC-72 carbon black, join in the conical flask that the 100ml isopropyl alcohol is housed, add the pyrroles of 3mmol and the distilled water of 100ml behind the ultrasonic dispersion 30min, add the hydrogen peroxide solution (H of the 30wt% of 1ml behind the stirring 30min
2O
2) solution, polymerisation 2h under the magnetic agitation then.Products therefrom filters the back with absolute ethyl alcohol and distilled water cyclic washing; 45 ℃ of dry 12h obtain the material with carbon element of surperficial PPy coating decoration then; Itself and 0.4g Diaquaoxalato cobalt are joined in the conical flask that the 200ml distilled water is housed; Stir 2.5h behind the ultrasonic dispersion 1h, be transferred to subsequently in the round-bottomed flask, pass through the rotary evaporation solvent evaporated down in water bath with thermostatic control.Be transferred to products therefrom in the quartz boat then and place the tube furnace of nitrogen protection, keep 1.5h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get CATALYST Co-PPy-H
2O
2/ XC72-old.
Comparative example 4:
Take by weighing 0.6g Black Pears 2000 (BP2000) carbon black; Join in the conical flask that the 100ml isopropyl alcohol is housed; Add the pyrroles of 3mmol and the distilled water of 100ml behind the ultrasonic dispersion 30min; Ammonium persulfate (APS) solution and the p-methyl benzenesulfonic acid (TsOH) of 0.19g, the polymerisation 4h under the magnetic agitation then that add the 0.06mol/L of 100ml behind the stirring 30min.Products therefrom filters the back with absolute ethyl alcohol and distilled water cyclic washing; 45 ℃ of dry 12h obtain the material with carbon element of surperficial PPy coating decoration then; Itself and 0.32g nine nitric hydrate iron are joined in the conical flask that the 200ml distilled water is housed; Stir 2h behind the ultrasonic dispersion 1h, be transferred to subsequently in the round-bottomed flask, pass through the rotary evaporation solvent evaporated down in water bath with thermostatic control.Be transferred to products therefrom in the quartz boat then and place the tube furnace of nitrogen protection, keep 2h after rising to 800 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get catalyst Fe-PPy-TsOH-APS/BP2000-old.
Comparative example 5:
Take by weighing 0.8g Vulcan XC-72 carbon black, join in the conical flask that the 100ml isopropyl alcohol is housed, add the pyrroles of 5mmol and the distilled water of 100ml behind the ultrasonic dispersion 30min, add the hydrogen peroxide solution (H of the 30wt% of 1ml behind the stirring 30min
2O
2) solution, polymerisation 5h under the magnetic agitation then.Products therefrom filters the back with absolute ethyl alcohol and distilled water cyclic washing; 45 ℃ of dry 12h obtain the material with carbon element of surperficial PPy coating decoration then; Itself and 0.56g five oxalic acid hydrate iron are joined in the conical flask that the 200ml distilled water is housed; Stir 2h behind the ultrasonic dispersion 1h, be transferred to subsequently in the round-bottomed flask, pass through the rotary evaporation solvent evaporated down in water bath with thermostatic control.Be transferred to products therefrom in the quartz boat then and place the tube furnace of nitrogen protection, keep 3h after rising to 900 ℃ with the heating rate of 5 ℃/min, under nitrogen protection, cool to room temperature at last with the furnace and promptly get catalyst Fe-PPy-H
2O
2/ XC72-old.
Embodiment 6
A kind of preparation method of carbon-supported metal polypyrrole class oxygen reduction catalyst; This method may further comprise the steps: a certain amount of Diaquaoxalato cobalt is dissolved in the aqueous solvent; Adding CNT then evenly disperses therein; Add the pyrroles again, fully stir the back and add oxidant ammonium persulfate and adulterant p-methyl benzenesulfonic acid, polymerisation 0.1h under stirring condition then; Be transferred to after the products therefrom drying that heat treatment 10h promptly makes the target catalyst in 300 ℃ of hot environments of nitrogen protection; The mol ratio of employed pyrroles and oxidant is 20: 1 in this process; Ratio between the milliliter number of pyrroles's mM number and solvent is 1: 15; The mol ratio of pyrroles and adulterant is 1: 1, is 100% in the gross mass of pyrroles, oxalates cobalt and carbon fiber, and pyrroles's quality is 30%; The quality of contained cobalt is 13wt% in the Diaquaoxalato cobalt, and the quality of carbon fiber is 29.68%.
Embodiment 7
A kind of preparation method of carbon-supported metal polypyrrole class oxygen reduction catalyst; This method may further comprise the steps: with a certain amount of nine nitric hydrate dissolved ferric irons in the solvent isopropyl alcohol; Adding charcoal-aero gel then evenly disperses therein; Add the pyrroles again, fully stir the back and add oxidant trivalent iron salt and adulterant DBSA, polymerisation 8h under stirring condition then; Be transferred to after the products therefrom drying that heat treatment 0.1h promptly makes the target catalyst in 1200 ℃ of hot environments of argon shield; The mol ratio of employed pyrroles and oxidant is 1: 15 in this process; Ratio between the milliliter number of pyrroles's mM number and solvent is 1: 120; The mol ratio of pyrroles and adulterant is 25: 1, is 100% in the gross mass of pyrroles, metal precursor and material with carbon element, and pyrroles's quality is 5%; The quality of contained iron is 0.02wt% in the nine nitric hydrate iron, and the quality of charcoal-aero gel is 94.85%.
Need to prove; The invention is not restricted to the foregoing description; Any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses, and the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention; Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. the preparation method of a carbon-supported metal polypyrrole class oxygen reduction catalyst; It is characterized in that; This method may further comprise the steps: a certain amount of metal precursor is dissolved in the solvent, adds material with carbon element then and evenly disperse therein, add the pyrroles again; Fully stir the back and add oxidant, polymerisation 0.1-8h under stirring condition then; Be transferred to after the products therefrom drying that heat treatment 0.1-10h promptly makes the target catalyst in the hot environment of inert atmosphere protection; The pyrroles who uses in the catalyst preparation process and the mol ratio of oxidant are 20: 1-1: 15; Ratio between the milliliter number of pyrroles's mM number and solvent is 1: 15-1: 120; Gross mass in pyrroles, metal precursor and material with carbon element is 100%; Pyrroles's quality is 5-30%, and the quality of contained metal is 0.02-13% in the metal precursor, and the quality of material with carbon element is 20-99.9%.
2. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that contained metal is cobalt or iron in the described metal precursor.
3. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that, described metal precursor is oxalates, acetate, nitrate, sulfate or the chloride of metal.
4. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that described solvent is water, isopropyl alcohol, ethanol, ethylene glycol or pyridine.
5. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that, described material with carbon element is carbon black, carbon fiber, CNT, charcoal-aero gel, active carbon, Graphene or its mixture.
6. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that described oxidant is ammonium persulfate, hydrogen peroxide solution or trivalent iron salt.
7. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that, also can add adulterant when adding oxidant, and the addition of adulterant is: the mol ratio of pyrroles and adulterant is 1: 1-25: 1.
8. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 7 is characterized in that described adulterant is benzene sulfonic acid, p-methyl benzenesulfonic acid, DBSA, naphthalene sulfonic acids and salt thereof and derivative.
9. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that described inert gas is nitrogen or argon gas.
10. the preparation method of a kind of carbon-supported metal polypyrrole class oxygen reduction catalyst according to claim 1 is characterized in that heat treated temperature is 300-1200 ℃ in the described hot environment.
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| CN118299594A (en) * | 2024-04-02 | 2024-07-05 | 天津大学 | Tripyrrole-N precisely coordinated monoatomic material, preparation method thereof and application thereof in fuel cell |
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| CN103626152A (en) * | 2013-11-27 | 2014-03-12 | 广东电网公司电力科学研究院 | Modification method of carbon nano tube |
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| CN115207378A (en) * | 2022-07-25 | 2022-10-18 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
| CN115207378B (en) * | 2022-07-25 | 2023-09-05 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
| CN118299594A (en) * | 2024-04-02 | 2024-07-05 | 天津大学 | Tripyrrole-N precisely coordinated monoatomic material, preparation method thereof and application thereof in fuel cell |
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