CN102631915A - Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst - Google Patents
Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst Download PDFInfo
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- CN102631915A CN102631915A CN2011104300321A CN201110430032A CN102631915A CN 102631915 A CN102631915 A CN 102631915A CN 2011104300321 A CN2011104300321 A CN 2011104300321A CN 201110430032 A CN201110430032 A CN 201110430032A CN 102631915 A CN102631915 A CN 102631915A
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Abstract
The invention discloses a fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and a preparation method and application of the fuel-cell catalyst. The preparation method of the fuel-cell catalyst is characterized by being simple in process and environment-friendly. According to the preparation method, acidification modification and/or alkalization modification are/is performed on intermediate-phase carbon microspheres to introduce some polarity function groups on the surfaces of catalyst carriers to remarkably enlarge the superficial area of the catalyst carriers and improve the adsorptive capacity of the catalyst carriers, so that the adsorbance of the catalyst is enlarged remarkably, the capacity and the dispersion degree of platinum in the catalyst carriers are controlled effectively, the catalytic performance of the Pt is improved, the utilization rate of the noble metal catalyst is enhanced, and the problems of poor stability, poor durability, high cost and the like of the fuel-cell catalyst carriers are effectively solved; in addition, the prepared fuel-cell catalyst with the intermediate-phase carbon microspheres load Pt has the advantages of being excellent in catalytic performance, low in cost, corrosion-resisting, good in durability, excellent in stability, and the like.
Description
Technical field
The invention belongs to the fuel-cell catalyst field, fuel-cell catalyst of particularly a kind of MCMB supporting Pt and preparation method thereof and its application.
Background technology
Under the deficient day by day situation of current fossil energy, fuel cell receives much attention as another the new chemical energy after thermoelectricity, wind-powered electricity generation, nuclear power and regenerative resource.Advantage such as wherein, the pem cell in the fuel cell has efficiently, environmental friendliness, low noise, reliability are high, easy to maintenance and by broad research.Proton Exchange Membrane Fuel Cells is with hydrogen (H
2) be fuel, H
2Under the catalytic action of GND catalyst, oxidation discharges hydrogen proton (H
+) and electronics, H
+Arrive anode through PEM, electronics flows to anodal through external circuit, thereby forms electric current; Anodal reactant is airborne oxygen (O
2), oxygen is caught by way of the electronics of external circuit and is reduced under the catalytic action of anode catalyst, simultaneously and H
+In conjunction with generating water (H
2O).
At present, the catalyst in the fuel cell still is main noble metal catalyst with the platinum metal, and these noble metal catalysts all have catalytic activity to the redox reaction of anodal and negative pole.But platinum metal costs an arm and a leg, resource-constrained, and the method that the method that needs research to improve its utilization rate perhaps reduces its consumption reduces its manufacturing cost.For this reason; Existing platinum group metal catalysts all with the form high degree of dispersion of nano particle on the catalyst carrier of high-specific surface area; Wherein, known catalyst carrier comprises carbon carrier and/or other carriers such as CNT, Graphene, carbon black, carbon aerogels, ordered mesopore carbon.But; These catalyst carriers cause the decline of catalyst carrier because of electrochemical corrosion resistant not; There are defectives such as poor stability and poor durability, and still have problems such as cost height, poor stability and poor durability, greatly hindered the commercialization process of fuel cell.
For problems such as the stability that solves catalyst carrier and durability, people such as Li Yunxia (Acta PhySico-Chimica Sinica, 2011; 27 (4): 858-862) adopt the direct chemical reducing process to prepare Graphene (Gr) loaded Pt catalyst; Its result of study shows that the Pt/Gr catalyst of being done the catalyst carrier preparation by Graphene has dispersiveness preferably, and; The good electric conductivity of Gr makes Pt on the Gr of lamellar structure, have higher utilization rate; And there is synergistic function between the surface-active center of Gr and the Pt catalyst, can significantly improves the catalytic efficiency of Pt/Gr catalyst, and significantly improved the redox reaction efficient in the fuel cell; Its catalytic efficiency even be superior to the JM-Pt/C electrode (wherein, the JM-Pt/C electrode is by Britain Jonhson-Matthey manufactured) of commercial applications.But, the complicated process of preparation of Graphene, and have potential safety hazard, and cost an arm and a leg, so still exist production cost high, be unfavorable for defectives such as large-scale production.CN102110821A discloses a kind of fuel battery negative pole (negative pole) catalyst that is applicable to the high stability of dynamic operation condition; This catalyst has used pretreated made of carbon nanotubes, and to carry the Pt amount be 20% Pt/CNT catalyst, and the stability that has significantly improved catalyst and its electrochemically resistant are learned the ability of corrosion.But the specific area of CNT is little, and is relatively poor with the adhesion of other materials, and costs an arm and a leg, and exists production cost high, is unfavorable for defectives such as large-scale production.CN101229512A discloses a kind of method that improves fuel cell catalyst stability; This method is through carrying out high-temperature heat treatment to carbon carrier; Make carbon support material part graphitization; Improve the stability of carbon carrier, the more graphited carbon carrier of part has been carried out acid treatment, adopted the method for directly reduction or reduction of ethylene glycol that Pt is loaded on the carrier again.This method improves the stability of carrier through the part graphitization processing of carbon support material, has overcome the problems such as catalyst loss, poor durability and poor stability that caused by electrochemical corrosion to a certain extent.But the catalyst of this method preparation exists still that the adhesion between Pt and the carbon carrier is poor, the Pt nano particle is easily in carrier surface migration, defectives such as reunion is grown up, surface area reduces, catalytic activity reduction.For this reason, need the fuel-cell catalyst carrier that a kind of stability of research is better, durability is more excellent, cost is more excellent.
Summary of the invention
The object of the present invention is to provide a kind of fuel-cell catalyst of MCMB supporting Pt; Described fuel-cell catalyst is a carrier with the pretreated MCMB of activation; Wherein, adopt electronation sedimentation or electrochemical deposition method that Pt salt is reduced to the Pt metal and it is loaded on the pretreated MCMB carrier of activation, the preparation method of said fuel-cell catalyst comprises the steps: 1) MCMB is carried out after pre-activated handles; Adding water cleans near neutral; Oven dry, cooling makes the pretreated MCMB of activation; Wherein, described pre-activated is handled any or its combination that is selected from acidified modified processing, alkalization modified processing; 2) MCMB after the activation processing that step 1) is made places water, stirs, and makes the carbon slurry, slowly adds the platinum salting liquid; Make its with activation processing after MCMB fully mix, add reductant solution again, regulator solution pH is heated to 40 ℃-90 ℃ near neutral; Insulation 20min-60min, be cooled to room temperature after, continue to stir 12h-24h, filter; Clean, oven dry promptly gets.
In the optimal technical scheme of the present invention, the meta particle diameter (D50) of said MCMB is 1-100 μ m, is preferably 10-40 μ m, more preferably 10-20 μ m.
In the optimal technical scheme of the present invention, the wet concentration described in the preparation process of fuel-cell catalyst is from any or its combination of distilled water, deionized water, pure water.
In the optimal technical scheme of the present invention, the acidified modified of said MCMB is selected from nitric acid, H with material
2O
2, phosphoric acid, sulfuric acid, hydrochloric acid any or its combination, be preferably nitric acid: the mass ratio of hydrogen peroxide solution is 0.8-1.5: 1 nitric acid hydrogen peroxide solution.
In the optimal technical scheme of the present invention; The alkalization modified processing of said MCMB is selected from any or its combination of solubility hydroxide, carbonate, bicarbonate, phosphate, hydrophosphate, the dihydric phosphate of solubility hydroxide, the potassium of sodium with material, be preferably any or its combination of NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the mass percent concentration of acidified modified solution is 40-75%, is preferably 50-70%, more preferably 60-65%.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the mass ratio between said acidified modified material and the MCMB is 1-15: 1, be preferably 5-12: and 1,8-10 more preferably: 1.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the acidified modified processing time is 0.5h-6h, is preferably 1h-5h, more preferably 2-3h.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the mass percent concentration of alkalization modified solution is 10%-50%, is preferably 20%-40%, more preferably 28%-32%.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the mass ratio between said alkalization modified material and the MCMB is 1-50: 1, be preferably 10-40: and 1,30-35 more preferably: 1.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the alkalization modified processing time is 0.5h-6h, is preferably 1h-5h, more preferably 2-3h.
In the optimal technical scheme of the present invention, the mass ratio between MCMB after the activation processing and the platinum salt is 1.6-6.4: 1, be preferably 2.1-4.0: and 1, more preferably 3.2: 1.
In the optimal technical scheme of the present invention, step 2) stirring described in is selected from any or its combination of sonic oscillation, mechanical agitation, magnetic agitation.
In the optimal technical scheme of the present invention, the Pt salt material of forming said platinum salting liquid is selected from chloroplatinic acid, potassium chloroplatinate, platinic sodium chloride, platinum tetrachloride, hydroxyl sodium platinate, [Pt (NO
2)
2(NH
3)
2], any or its combination of platinum nitrate, be preferably chloroplatinic acid.
In the optimal technical scheme of the present invention; The material of regulator solution pH is selected from any or its combination of NaOH, KOH, sodium acid carbonate, saleratus, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, is preferably any or its combination of NaOH, KOH.
In the optimal technical scheme of the present invention; The reducing agent material of forming said reductant solution is selected from any or its combination of formaldehyde, ethylene glycol, sodium borohydride, natrium citricum, sodium hypophosphite, sodium formate, paraformaldehyde, ascorbic acid, is preferably any or its combination of sodium hypophosphite, formaldehyde, ethylene glycol.
In the optimal technical scheme of the present invention, the mass percent concentration of said reductant solution is 10%-50%, is preferably 20%-40%, more preferably 28%-32%.
In the optimal technical scheme of the present invention, the mass ratio between reducing agent and the platinum salt is 20-200: 1, be preferably 80-180: and 1,100-150 more preferably: 1.
The fuel-cell catalyst of MCMB supporting Pt of the present invention is novel fuel-cell catalyst, and said catalyst is a carrier material with the pretreated MCMB of activation.Find that through scanning electron microscope analysis the precious metals pt uniform particles in the fuel-cell catalyst carrier of MCMB supporting Pt of the present invention is deposited on the MCMB, has improved the decentralization of precious metals pt at carrier surface; Significantly improved the utilization rate of catalyst; And the MCMB material has good anti-corrosion, comprises the ability of electrochemical corrosion resistant; The stability and the durability of Pt/C composite have significantly been improved, significant prolongation its service life.
MCMB of the present invention is a kind of of Delanium; Described MCMB with mink cell focus, pitch (wherein; Said pitch comprises mid temperature pitch, secondary coal tar pitch, asphalt etc.), residual oil, coal tar, secondary petroleum heavy oil, carbolineum, polycyclic aromatic hydrocarbon etc. are the preparation raw material; Can adopt preparation method known in the art to prepare; As too the grain size analysis and the structural research disclosed method of equality people (material science and technology, 2007,15 (3)) diauxic growth MCMB prepare to adopt Lee.The disclosed content of these documents is all as the application's reference.Wherein, the preparation of MCMB has not only realized the efficient trans-utilization of these raw materials, and the MCMB particle diameter that makes is evenly distributed; And, described MCMB have good electrical conductivity and chemical stability, high surface, low manufacturing cost, corrosion-resistant, electrochemically resistant learn the burn into environmental protection, through still having preferably advantage such as adhesion after the activation processing, and its particle is spheroidal or type spherical; Being easy to ion inserts from every side; Effectively improve the degree of scatter of catalyst, in case of necessity, can carry out activation processing it at carrier surface; Wherein, Described activation processing comprises acidified modified processing and/or alkalization modified processing, thereby introduces some polar functionalities groups on its surface, enlarges markedly its surface area; Improve its adsorption capacity; And enlarge markedly the adsorbance of catalyst and change it into desirable catalyst carrier, effectively improve the utilization rate of noble metal catalyst, effectively solve problems such as the existing poor stability of fuel-cell catalyst carrier, poor durability, cost height.
The object of the present invention is to provide a kind of preparation method of fuel-cell catalyst of MCMB supporting Pt; Described fuel-cell catalyst is a carrier with the pretreated MCMB of activation; Wherein, employing electronation sedimentation or electrochemical deposition method are reduced to the Pt metal with Pt salt and it are loaded on the pretreated MCMB carrier of activation, comprise following preparation process: after 1) MCMB being carried out the pre-activated processing; Adding water cleans near neutral; Oven dry, cooling makes the pretreated MCMB of activation; Wherein, described pre-activated is handled any or its combination that is selected from acidified modified processing, alkalization modified processing; 2) MCMB after the activation processing that step 1) is made places water, stirs, and makes the carbon slurry, slowly adds the platinum salting liquid; Make its with activation processing after MCMB fully mix, add reductant solution again, regulator solution pH is heated to 40 ℃-90 ℃ near neutral; Insulation 20min-60min, be cooled to room temperature after, continue to stir 12h-24h, filter; Clean, oven dry promptly gets.
In the optimal technical scheme of the present invention, the meta particle diameter (D50) of said MCMB is 1-100 μ m, is preferably 10-40 μ m, more preferably 10-20 μ m.
In the optimal technical scheme of the present invention, the wet concentration described in the preparation process of fuel-cell catalyst is from any or its combination of distilled water, deionized water, pure water.
In the optimal technical scheme of the present invention, the acidified modified of said MCMB is selected from nitric acid, H with material
2O
2, phosphoric acid, sulfuric acid, hydrochloric acid any or its combination, be preferably nitric acid: the mass ratio of hydrogen peroxide solution is 0.8-1.5: 1 nitric acid hydrogen peroxide solution.
In the optimal technical scheme of the present invention; The alkalization modified processing of said MCMB is selected from any or its combination of solubility hydroxide, carbonate, bicarbonate, phosphate, hydrophosphate, the dihydric phosphate of solubility hydroxide, the potassium of sodium with material, be preferably any or its combination of NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the mass percent concentration of acidified modified solution is 40-75%, is preferably 50-70%, more preferably 60-65%.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the mass ratio between said acidified modified material and the MCMB is 1-15: 1, be preferably 5-12: and 1,8-10 more preferably: 1.
In the optimal technical scheme of the present invention, in the said acidified modified treatment step, the acidified modified processing time is 0.5-6h, is preferably 1-5h, more preferably 2-3h.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the mass percent concentration of alkalization modified solution is 10-50%, is preferably 20-40%, more preferably 28-32%.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the mass ratio between said alkalization modified material and the MCMB is 1-50: 1, be preferably 10-40: and 1,30-35 more preferably: 1.
In the optimal technical scheme of the present invention, in the said alkalization modified treatment step, the alkalization modified processing time is 0.5-6h, is preferably 1-5h, more preferably 2-3h.
In the optimal technical scheme of the present invention, the mass ratio between MCMB after the activation processing and the platinum salt is 1.6-6.4: 1, be preferably 2.1-4.0: and 1, more preferably 3.2: 1.
In the optimal technical scheme of the present invention, step 2) stirring described in is selected from any or its combination of sonic oscillation, mechanical agitation, magnetic agitation.
In the optimal technical scheme of the present invention, the Pt salt material of forming said platinum salting liquid is selected from chloroplatinic acid, potassium chloroplatinate, platinic sodium chloride, platinum tetrachloride, hydroxyl sodium platinate, [Pt (NO
2)
2(NH
3)
2], any or its combination of platinum nitrate, be preferably chloroplatinic acid.
In the optimal technical scheme of the present invention; The material of regulator solution pH is selected from any or its combination of NaOH, KOH, sodium acid carbonate, saleratus, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, is preferably any or its combination of NaOH, KOH.
In the optimal technical scheme of the present invention; The reducing agent material of forming said reductant solution is selected from any or its combination of formaldehyde, ethylene glycol, sodium borohydride, natrium citricum, sodium hypophosphite, sodium formate, paraformaldehyde, ascorbic acid, is preferably any or its combination of sodium hypophosphite, formaldehyde, ethylene glycol.
In the optimal technical scheme of the present invention, the mass percent concentration of said reductant solution is 10-50%, is preferably 20-40%, more preferably 28-32%.
In the optimal technical scheme of the present invention, the mass ratio between reducing agent and the platinum salt is 20-200: 1, be preferably 80-180: and 1,100-150 more preferably: 1.
In the optimal technical scheme of the present invention, the said nearly neutrality of step (2) comprises the pH6.0-8.0 of solution, is preferably pH6.5-7.5.
The preparation method of MCMB supporting Pt fuel-cell catalyst of the present invention has characteristics such as technology is simple, environmental friendliness; And the MCMB supporting Pt fuel-cell catalyst that makes has catalytic performance excellence, cheap, corrosion-resistant, advantages such as durability good, excellent in stability.
The object of the present invention is to provide the pretreated MCMB of activation to be used for preparing the application of the fuel-cell catalyst of MCMB supporting Pt.
The object of the present invention is to provide a kind of pretreated method of activation of MCMB, described pre-activated processing method comprises any or its combination of acidified modified processing, alkalization modified processing.
In order clearly to explain protection scope of the present invention, the present invention defines term as follows:
The fuel-cell catalyst of MCMB supporting Pt of the present invention; Claim again in " Pt/C composite " or " carbon microspheres supporting Pt fuel-cell catalyst ", be meant and adopt the electronation deposition process that platinum salt is reduced to that Pt simple substance loads on the MCMB and the Pt/C composite that makes.
Activation processing of the present invention; Claim again " pre-activated processing ", comprise acidified modified processing and/or alkalization modified processing, thereby introduce some polar functionalities groups on the surface of MCMB carrier to MCMB; To enlarge markedly its surface area and to improve its adsorption capacity; Thereby enlarge markedly the adsorbance of catalyst, effectively improve the utilization rate of noble metal catalyst, effectively solve problems such as the existing poor stability of fuel-cell catalyst carrier, poor durability, cost height.
Acidified modified processing of the present invention is meant adopts acidic materials and/or oxidizer treatment MCMB; Introduce some polar functional groups on its surface; To enlarge markedly its surface area and to improve its adsorption capacity, enlarge markedly adsorbance to catalyst, effectively control the load capacity and the degree of scatter of platinum in the catalyst carrier; Improve the catalytic performance of Pt, improve the utilization rate of noble metal catalyst.
Alkalization modified processing of the present invention is meant adopts the alkaline matter for processing MCMB; Introduce some polar functional groups on its surface; To enlarge markedly its surface area and to improve its adsorption capacity, enlarge markedly adsorbance to catalyst, effectively control the load capacity and the degree of scatter of platinum in the catalyst carrier; Improve the catalytic performance of Pt, improve the utilization rate of noble metal catalyst.
JM-Pt/C catalyst of the present invention is meant the Pt/C composite by Britain Jonhson-Matthey manufactured, and wherein, the carbon carrier in the composite is a Vulcan XC-72 carbon, and this catalyst and electrode thereof be commercial applications.
Meta particle diameter of the present invention (D50) is meant that the cumulative particle sizes percentile of sample reaches 50% o'clock pairing particle diameter; Wherein, The present invention adopts laser method to measure the D50 of MCMB, as selects for use MASTERSIZER 2000 analyzers to measure the D50 of MCMB.
The present invention adopts the cyclic voltammetric method of testing to detect the stability of catalyst carrier, promptly through test with the hydrogen reduction current density after calculating electrode scanning 1000 circles and attenuation degree thereof the stability that draws catalyst carrier.
The present invention adopts linear sweep voltammetry to study the catalytic activity of MCMB supported catalyst; Promptly adopt linear sweep voltammetry that the electrode of processing with the MCMB platinum catalyst is tested; The hydrogen reduction current density of gained polarization curve is promptly reacted the catalytic activity of carbon microspheres supported catalyst; Wherein, the hydrogen reduction current density is big more, explains that catalytic activity is good more.
Nearly neutrality according to the invention is meant the pH6.0-8.0 of solution, is preferably pH6.5-7.5.
ρ of the present invention (Pt) refers to that platinum salt is (like H
2PtCl
6) only comprise the concentration of Pt element in the solution.
Except as otherwise noted, when the present invention relates to the percentage between liquid and the liquid, described percentage is volume percentage; When the present invention relates to the percentage between liquid and the solid, said percentage is volume/weight percentage; When the present invention relates to the percentage between solid and the liquid, said percentage is weight/volume percent; All the other are weight/percentage by weight.
Compared with prior art, the present invention has following advantage:
1, among the fuel-cell catalyst preparation method of MCMB supporting Pt according to the invention; Through MCMB is carried out activation processing; Comprise acidified modified processing and/or alkalization modified processing, and the addition and the processing time of preferred acidifying modified material and/or alkalization modified material, thereby some polar functionalities groups introduced on the surface of catalyst carrier; Enlarging markedly its surface area and to improve its adsorption capacity, thereby enlarge markedly the adsorbance of catalyst; And; The concentration of preferred reducing substances of the present invention and/or platinum salt, reductant solution, the parameters such as reduction processing time of platinum salt; Effectively control the load capacity and the degree of scatter of platinum in the catalyst carrier; Effectively improve the catalytic performance of Pt, improve the utilization rate of noble metal catalyst, effectively solve problems such as the existing poor stability of fuel-cell catalyst carrier, poor durability, cost height;
2, the fuel-cell catalyst of the MCMB supporting Pt that makes of the present invention has catalytic performance excellence, cheap, corrosion-resistant, advantages such as durability good, excellent in stability;
3, the preparation method of the fuel-cell catalyst of MCMB supporting Pt of the present invention has characteristics such as technology is simple, environmental friendliness.
Description of drawings
Process the cyclic voltammetry curve of electrode in Fig. 1 comparative studies embodiment 1 and the Comparative Examples 1, wherein, abscissa is the voltage with respect to the Ag/AgCl reference electrode, and ordinate is a current density.
Process the polarization of electrode curve in Fig. 2 comparative studies embodiment 1 and the Comparative Examples 1, wherein, abscissa is the voltage with respect to the Ag/AgCl reference electrode, and ordinate is a current density.
The specific embodiment
Below will combine embodiment to specify the present invention, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1The preparation of fuel-cell catalyst pem fuel electrode of the present invention
The preparation of the fuel-cell catalyst pem fuel electrode of MCMB supporting Pt of the present invention comprises the steps:
(1) activation processing of MCMB
Take by weighing the 2g MCMB, it is inserted in the NaOH aqueous solution that 20ml concentration is 30wt% vibrating dispersion 1h; To being uniformly dispersed, clean near neutral, under 80 ℃ of conditions with distilled water; Vacuum drying 12h is cooled to room temperature, makes the MCMB after the alkalization modified processing;
(2) preparation of carbon microspheres supporting Pt fuel-cell catalyst (claiming the Pt/C composite again)
Take by weighing the MCMB after the alkalization modified processing that 500mg step (1) makes, be placed in the 20ml water, sonic oscillation 15min makes the carbon slurry, and slowly adding 10ml ρ (Pt) concentration more therein is the H of 7.4mg/ml
2PtCl
6, it is fully mixed with MCMB, add 60ml concentration again and be 30% sodium hypophosphite solution, add appropriate amount of NaOH solution; Regulate previous reaction solution near neutral, be heated to 60 ℃, insulation 30min; After being cooled to room temperature, continue to stir 20h, filter; Clean, 80 ℃ of oven dry promptly get the Pt/C composite;
(3) preliminary treatment of carbon paper
The carbon paper cutting is become the fritter that area is 3.1cm*2.4cm, again it is immersed in the ethanol water, sonic oscillation 30min;
(4) preparation Pt/C catalyst electrode
Take by weighing MCMB platinum catalyst and perfluorinated sulfonic resin that step (2) makes respectively; Wherein, The MCMB platinum catalyst: the mass ratio of perfluorinated sulfonic resin is 3: 1; The mass concentration of perfluorinated sulfonic resin is 5%, and the platinum content in the control Pt/C catalyst electrode is 0.1mg/cm
2, be solvent with ethanol, sonic oscillation mixes to it, and it repeatedly is uniformly coated on the pretreated carbon paper of step (3), and 60 ℃ of oven dry make the pem fuel electrode.
Embodiment 2The preparation of cell catalyst pem fuel electrode of the present invention
The preparation of the fuel-cell catalyst pem fuel electrode of MCMB supporting Pt of the present invention comprises the steps:
(1) activation processing of MCMB
Take by weighing the 2g MCMB, with nitric acid H
2O
2In the water mixed solution, wherein, described nitric acid H
2O
2Water mixed solution is that 60% salpeter solution 50ml and mass percent concentration are 20% H by mass percent concentration
2O
2Aqueous solution 50ml forms, and vibrating dispersion 1h to being uniformly dispersed, cleans near neutral with distilled water, and under 80 ℃ of conditions, vacuum drying 12h naturally cools to room temperature, makes the MCMB after the acidified modified processing;
(2) preparation of carbon microspheres supporting Pt fuel-cell catalyst (claiming the Pt/C composite again)
Take by weighing the MCMB after the activation processing that 500mg step (1) makes, be placed in the 20ml water, sonic oscillation 15min makes the carbon slurry, slowly adds 10ml ρ (Pt) more therein and is the H of 7.4mg/ml
2PtCl
6, it is fully mixed with carbon microspheres, add 60ml concentration again and be 30% sodium hypophosphite solution, add appropriate amount of NaOH solution; Regulate previous reaction solution near neutral, be heated to 60 ℃, insulation 30min; After being cooled to room temperature, continue to stir 20h, filter; Clean, 80 ℃ of oven dry promptly get the Pt/C composite;
(3) preliminary treatment of carbon paper
The carbon paper cutting is become the fritter that area is 3.1cm*2.4cm, again it is immersed in the ethanol water, sonic oscillation 30min;
(4) preparation Pt/C catalyst electrode
Take by weighing MCMB platinum catalyst and perfluorinated sulfonic resin that step (2) makes respectively; Wherein, The MCMB platinum catalyst: the mass ratio of perfluorinated sulfonic resin is 3: 1; The mass concentration of perfluorinated sulfonic resin is 5%, and the platinum content in the control Pt/C catalyst electrode is 0.1mg/cm
2, be solvent with ethanol, sonic oscillation mixes to it, and it repeatedly is uniformly coated on the pretreated carbon paper of step (3), and 60 ℃ of oven dry make the pem fuel electrode.
Embodiment 3The preparation of MCMB supporting Pt fuel-cell catalyst pem fuel electrode
The preparation of the fuel-cell catalyst pem fuel electrode of MCMB supporting Pt of the present invention comprises the steps:
(1) the alkalization modified processing (activation processing) of MCMB
Take by weighing the 2g MCMB, putting it into 20ml concentration is in the NaOH aqueous solution of 30wt%, and vibration mixes 1h; To mixing, clean near neutral, under 80 ℃ of conditions with distilled water; Vacuum drying 12h naturally cools to room temperature, obtains the MCMB after the alkalization modified processing;
(2) preparation of carbon microspheres supporting Pt fuel-cell catalyst (claiming the Pt/C composite again)
Take by weighing the MCMB after the activation processing that 500mg step (1) makes, be placed in the 20ml water, sonic oscillation 15min makes the carbon slurry, slowly adds 10ml ρ (Pt) more therein and is the H of 7.4mg/ml
2PtCl
6, it is fully mixed with carbon microspheres, add 60ml concentration again and be 60% ethylene glycol solution, add appropriate amount of NaOH solution; Regulate previous reaction solution near neutral, be heated to 60 ℃, insulation 30min; After being cooled to room temperature, continue to stir 20h, filter; Clean, 80 ℃ of oven dry promptly get the Pt/C composite;
(3) preliminary treatment of carbon paper
The carbon paper cutting is become the fritter that area is 3.1cm*2.4cm, again it is immersed in the ethanol water, sonic oscillation 30min;
(4) preparation Pt/C catalyst electrode
Take by weighing MCMB platinum catalyst and perfluorinated sulfonic resin that step (2) makes respectively; Wherein, The MCMB platinum catalyst: the mass ratio of perfluorinated sulfonic resin is 3: 1; The mass concentration of perfluorinated sulfonic resin is 5%, and the platinum content in the control Pt/C catalyst electrode is 0.1mg/cm
2, be solvent with ethanol, sonic oscillation mixes to it, and it repeatedly is uniformly coated on the pretreated carbon paper of step (3), and 60 ℃ of oven dry make the pem fuel electrode.
Comparative Examples 1The preparation of JM-Pt/C catalyst pem fuel electrode
The preparation of JM-Pt/C catalyst pem fuel electrode of the present invention comprises the steps:
(1) preliminary treatment of carbon paper
The carbon paper cutting is become the fritter that area is 3.1cm*2.4cm, again it is immersed in the ethanol water, sonic oscillation 30min.
(2) preparation Pt/C catalyst electrode
Take by weighing Pt/C catalyst (Britain Jonhson-Matthey company respectively; Claim " JM-Pt/C " again) and perfluorinated sulfonic resin; Wherein, The Pt/C catalyst: the mass ratio of perfluorinated sulfonic resin is 3: 1, and the mass concentration of perfluorinated sulfonic resin is 5%, and the platinum content in the control Pt/C catalyst electrode is 0.1mg/cm
2, be solvent with ethanol, sonic oscillation mixes to it, and it repeatedly is uniformly coated on the pretreated carbon paper of step (1), and 60 ℃ of oven dry make the pem fuel electrode.
Embodiment 4The cyclic voltammetry curve of comparative studies embodiment 1-3 electrode and Comparative Examples 1 electrode
(wherein, the platinum content in two electrodes is 0.1mg/cm for Cyclic Voltammetry, the CV) cyclic voltammetry curve of detection embodiment 1-3 electrode and Comparative Examples 1 electrode to adopt cyclic voltammetry
2, the oxidation-reduction potential of measuring samples, the invertibity and the reaction mechanism of investigation electrochemical reaction.Adopt CHI660C to do the CV test among the present invention, with research oxidation-reduction process and invertibity, voltage scan range is-0.2～1.0V, and sweep speed is 0.1mV/s.Wherein, embodiment 1-3 electrode or Comparative Examples 1 electrode are respectively as working electrode, and reference electrode is the Ag/AgCl electrode, and platinum electrode is to electrode.Fig. 1 is the cyclic voltammetry curve result of embodiment 1 electrode.
Visible by Fig. 1; MCMB platinum catalyst electrode of the present invention is similar with the curve peak shape of JM-Pt/C catalyst electrode; Peak area is close; Show that MCMB platinum catalyst of the present invention has/similar catalytic activity basic identical with the JM-Pt/C catalyst, pre-activated of the present invention is handled the back MCMB and can be used as the catalyst Pt carrier, and prepared MCMB Pt/C compound has excellent catalytic activity.
Embodiment 5Comparative studies embodiment 1-3 electrode and Comparative Examples 1 polarization of electrode curve
Adopt linear sweep voltammetry test implementation example 1-3 and Comparative Examples 1 to process the polarization of electrode curve, wherein, the platinum content in two electrodes is 0.1mg/cm2.Linear sweep voltammetry adopts three-electrode system, on electrode, applies the voltage of a linear change, the curve that record current density changes with electrode potential, and scanning voltage is 0.2-1.0V, sweep speed is 0.1mV/s.Wherein, embodiment 1-3 electrode or Comparative Examples 1 electrode are respectively as working electrode, and reference electrode is the Ag/AgCl electrode, and platinum electrode is to electrode.Fig. 2 is embodiment 1 polarization of electrode curve result.
Visible by Fig. 2; The MCMB platinum catalyst electrode of the present invention's preparation and the polarization curve of JM commercialization Pt/C catalyst electrode are identical basically; Peak shape is similar; Show that the MCMB platinum catalyst that the present invention prepares has/similar redox property and catalytic activity identical with JM commercialization Pt/C catalyst, the pretreated MCMB of activation can be used as the catalyst Pt carrier, and prepared MCMB Pt/C compound has excellent catalytic activity.
Embodiment 6The stability of catalyst carrier and catalytic activity research
Stability, the catalytic activity of present embodiment research catalyst carrier; Wherein, According to embodiment 4 described cyclic voltammetric method of testings; The fuel cell catalyst electrode of the MCMB supporting Pt that makes of test the present invention, the stability of Pt/Vulcan XC-72 carbon (JM-Pt/C catalyst) electrode are studied its stability through the hydrogen reduction current density on the cyclic voltammetry curve behind test electrode scanning 1000 circles and with the attenuation degree of hydrogen reduction current density contrast on the 1st circle cyclic voltammetry curve, wherein; The hydrogen reduction current density is big more, explains that stability is good more; Adopt the catalytic activity of embodiment 5 said linear sweep voltammetry testing catalytic agent carriers, come catalytic reaction active according to the size of hydrogen reduction current density on the polarization curve, wherein, reduction current density is big more, and catalytic activity is good more.The result sees table 1.
The stability of table 1 catalyst carrier and catalytic activity result of study
Visible by table 1; Compare with Vulcan XC-72 carbon loaded Pt catalyst; The MCMB loaded Pt catalyst that the present invention makes has/similar catalytic activity basic identical with it as the catalyst of fuel cell; And its catalytic activity and stability are superior to JM-Pt/C slightly, also have tangible price advantage.
Claims (14)
1. the preparation method of the fuel-cell catalyst of a MCMB supporting Pt, described fuel-cell catalyst is a carrier with the pretreated MCMB of activation, wherein; Employing electronation sedimentation or electrochemical deposition method are reduced to the Pt metal with Pt salt and it are loaded on the pretreated MCMB carrier of activation; Comprise following preparation process: after 1) MCMB being carried out the pre-activated processing, add water and clean, dry near neutral; Cooling; Make the pretreated MCMB of activation, wherein, described pre-activated is handled any or its combination that is selected from acidified modified processing, alkalization modified processing; 2) MCMB after the activation processing that step 1) is made places water, stirs, and makes the carbon slurry, slowly adds the platinum salting liquid; Make its with activation processing after MCMB fully mix, add reductant solution again, regulator solution pH is heated to 40 ℃-90 ℃ near neutral; Insulation 20min-60min, be cooled to room temperature after, continue to stir 12h-24h, filter; Clean, oven dry promptly gets.
2. preparation method according to claim 1, the acidified modified of said MCMB is selected from nitric acid, H with material
2O
2, phosphoric acid, sulfuric acid, hydrochloric acid any or its combination, be preferably nitric acid: the mass ratio of hydrogen peroxide solution is 0.8-1.5: 1 nitric acid hydrogen peroxide mixed solution.
3. according to each described preparation method of claim 1-2; The alkalization modified processing of said MCMB is selected from any or its combination of solubility hydroxide, carbonate, bicarbonate, phosphate, hydrophosphate, the dihydric phosphate of solubility hydroxide, the potassium of sodium with material, be preferably any or its combination of NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus.
4. according to each described preparation method of claim 1-3, in the said acidified modified treatment step, the mass percent concentration of acidified modified solution is 40-75%, is preferably 50-70%, more preferably 60-65%.
5. according to each described preparation method of claim 1-4, in the said acidified modified treatment step, the mass ratio between said acidified modified material and the MCMB is 1-15: 1, be preferably 5-12: and 1,8-10 more preferably: 1.
6. according to each described preparation method of claim 1-5, in the said alkalization modified treatment step, the mass percent concentration of alkalization modified solution is 10%-50%, is preferably 20%-40%, more preferably 28%-32%.
7. according to each described preparation method of claim 1-9, in the said alkalization modified treatment step, the mass ratio between said alkalization modified material and the MCMB is 1-50: 1, be preferably 10-40: and 1,30-35 more preferably: 1.
8. according to each described preparation method of claim 1-7, the mass ratio between MCMB after the activation processing and the platinum salt is 1.6-6.4: 1, be preferably 2.1-4.0: and 1, more preferably 3.2: 1.
9. according to each described preparation method of claim 1-8, the Pt salt material of forming said platinum salting liquid is selected from chloroplatinic acid, potassium chloroplatinate, platinic sodium chloride, platinum tetrachloride, hydroxyl sodium platinate, [Pt (NO
2)
2(NH
3)
2], any or its combination of platinum nitrate, be preferably chloroplatinic acid.
10. according to each described preparation method of claim 1-9; The reducing agent material of forming said reductant solution is selected from any or its combination of formaldehyde, ethylene glycol, sodium borohydride, natrium citricum, sodium hypophosphite, sodium formate, paraformaldehyde, ascorbic acid, is preferably any or its combination of sodium hypophosphite, formaldehyde, ethylene glycol.
11. according to each described preparation method of claim 1-10, the mass percent concentration of said reductant solution is 10%-50%, is preferably 20%-40%, more preferably 28%-32%.
12. according to each described preparation method of claim 1-11, the mass ratio between reducing agent and the platinum salt is 20-200: 1, be preferably 80-180: 1,100-150 more preferably: 1.
13. the fuel-cell catalyst of a MCMB supporting Pt adopts each described method of claim 1-12 to prepare.
14. the pretreated MCMB of activation is used for preparing the application of the fuel-cell catalyst of each described MCMB supporting Pt of claim 1-12; Wherein, described pre-activated processing method comprises any or its combination of acidified modified processing, alkalization modified processing.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102960366A (en) * | 2012-12-05 | 2013-03-13 | 太原理工大学 | Preparation method of Ag-carrying carbon microsphere antibacterial agent |
| CN104741617A (en) * | 2013-12-31 | 2015-07-01 | 赵斌元 | Composite micro-nano silver powder and preparing method thereof |
| CN106252677A (en) * | 2016-08-03 | 2016-12-21 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of charcoal platinum catalyst |
| CN109560296A (en) * | 2017-09-27 | 2019-04-02 | 清远道动新材料科技有限公司 | Perovskite type catalyst and its preparation method and application, zinc air secondary cell |
| CN109841857A (en) * | 2019-02-25 | 2019-06-04 | 河南豫氢动力有限公司 | A kind of preparation method of the mesoporous Pt/C of fuel-cell catalyst |
| CN111129525A (en) * | 2019-12-30 | 2020-05-08 | 一汽解放汽车有限公司 | Carbon carrier for fuel cell, preparation method thereof and application thereof in fuel cell |
| CN112186199A (en) * | 2020-09-30 | 2021-01-05 | 中钢集团南京新材料研究院有限公司 | Catalyst for solid polymer fuel cell and preparation method thereof |
| CN113165076A (en) * | 2018-12-20 | 2021-07-23 | 出光兴产株式会社 | Method for producing composite body supporting metal and metal oxide |
| CN113745542A (en) * | 2021-09-15 | 2021-12-03 | 北京化工大学 | High platinum loading platinum/carbon catalyst for fuel cell and preparation method thereof |
| CN114388827A (en) * | 2021-12-16 | 2022-04-22 | 同济大学 | Batch preparation method of catalyst for fuel cell |
| CN114835115A (en) * | 2022-05-13 | 2022-08-02 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method and application of active mesophase carbon microspheres |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
-
2011
- 2011-12-07 CN CN2011104300321A patent/CN102631915A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
Non-Patent Citations (2)
| Title |
|---|
| G.SEVJIDSUREN ET AL.: "Effect of Different Support Morphologies and Pt Particle Sizes in Electrocatalysts for Fuel Cell Applications", 《JOURNAL OF NANOMATERIALS》 * |
| YI CHENG LIU ET AL.: "Methanol electro-oxidation on mesocarbon microbead supported Pt catalysts", 《CARBON》 * |
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Application publication date: 20120815 |