CN100503038C - Complex reduction method for preparing highly alloyed Pt-based compound metal nano catalyst - Google Patents
Complex reduction method for preparing highly alloyed Pt-based compound metal nano catalyst Download PDFInfo
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- CN100503038C CN100503038C CNB2005100402227A CN200510040222A CN100503038C CN 100503038 C CN100503038 C CN 100503038C CN B2005100402227 A CNB2005100402227 A CN B2005100402227A CN 200510040222 A CN200510040222 A CN 200510040222A CN 100503038 C CN100503038 C CN 100503038C
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Abstract
Complex reduction preparation method for high alloying Pt-based composition nano metal catalyst comprises: inject in precursor: add solution of Pt compound and other metal compound in carbon-carrier; mix and obtain constituent A; the other metals mean Ru, Os, Pd, Rh, Ir or Cr; take liquid-phase reduction at low temperature: add excessive reducer solution and mix, the reduced metal salt particles absorb on carbon carrier, and obtain constituent B; post process: bake and de-solvent to the constituent B, take bath in water and alcohol; dry at 40-150Deg, and obtain carbon carried PtM/C catalyst (M= Ru, Os, Pd, Rh, Ir or Cr). This invention changes electrode potential and reduces Pt and other metal at the same time to achieve the ordered sedimentation of multiple metals and improve alloying degree.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, be specifically related to a kind of catalyst of direct alcohol fuel battery---the complexing reducing preparation method of highly alloyed Pt-based composition metal nanocatalyst.This catalyst is to methyl alcohol, formic acid, H
2Presented very high catalytic performance with the electrochemical oxidation of CO mist and the electrical catalyze reduction of oxygen.
Background technology
Fuel cell becomes following best " clean energy resource " owing to have advantages such as energy conversion efficiency height, environmental pollution are little, and many national government are paid much attention to its research.Particularly direct alcohol fuel battery because it can be used as the electrical source of power and the portable removable power supply of electric vehicle, and is subjected to extensive concern in recent years.Directly alcohols fuel cell anode catalyst is the multiple catalyzing system of the alloying of Pt or Pt and other metal basically, but, because the price of these metals is extremely expensive, and resource-constrained, thereby cause battery to cost an arm and a leg, be difficult to carry out commercialization, therefore, people wish to improve as much as possible the activity of metallic catalyst and the cost that utilization rate reduces catalyst.
In DMFC, in general, the antianode catalyst has several basic requirements, promptly high electro catalytic activity, stability and electron conduction will be arranged.At present, anode catalyst is generally the platinum base alloy catalyst, but because the metal platinum price is more expensive, resource-constrained, must take effective measures the carrying capacity that reduces platinum, simultaneously, some intermediate products such as CO in the oxidation of alcohols process can make catalyst poisoning, and a spot of CO also can make catalyst poisoning in the reformation hydrogen.Therefore press for the carrying capacity that reduces platinum, prevent the intoxicating phenomenon of platinum.Polymolecularity, uniformity, the high-alloying of alloy atom bunch are necessary conditions of highly active catalyst, these platinum base alloy catalyst are preparing under hundreds of degree high temperature inert conditions usually, and the heat treatment under the high temperature has easily caused the agglomeration of metallic, thereby reduced the surface area of platinum base alloy, reduced the catalytic performance of catalyst.Simultaneously, even platinum base alloy cluster alloying level also is difficult to reach gratifying degree under hundreds of degree hot conditions.Therefore, exploring the method that can be used for the preparation of industrialization high performance catalyst is a problem that makes concern.
Summary of the invention
In conventional art, high-alloying platinum base alloy catalyst must prepare all deficiencies that caused under hundreds of degree high temperature inert conditions, the present invention will provide the new preparation method who can be used for suitability for industrialized production of this catalyst, new method should be able to improve the alloying level of composition metal, and obtaining to have the composite metal catalyst of less metal particle diameter, favorable uniformity and decentralization, the catalyst that makes shows very excellent electrocatalysis characteristic.
Technical scheme provided by the invention is: the complexing reducing preparation method of highly alloyed Pt-based composition metal nanocatalyst, it is a kind of new method for preparing high-alloying DMFC catalyst at low temperatures, its typical production is the injection of catalyst precursor in carbon carrier, the low temperature liquid phase reduction of presoma, and the post processing of catalyst.
Now that each step division is as follows:
1, the injection of catalyst precursor: add Pt compound and other solution of metal compound at carbon carrier, the Pt compound of adding and the amount of other metallic compounds account for 5～80% of carbon carrier amount.In said mixture, add the complexing agent mixed solution on this basis, stir to make and mix, component A, described other metallic compounds are: a kind of in Ru, Ir or the Cr compound;
2, low temperature liquid phase reduction: component A slowly adds excessive reductant solution and stirs under 0～80 ℃ of condition, the slaine particulate that restores is adsorbed on the carbon carrier, gets B component;
3, post processing part: the B component drying washes with water after removing and desolvating successively, alcohol is washed repeatedly, and 40～150 ℃ of dryings under certain atmosphere or vacuum condition then promptly make PtM/C (M=Ru, Ir, the Cr) catalyst of carbon carrier load.
The solution of described Pt compound is selected from H
2PtCl
6, K
2PtCl
6Or Na
2PtCl
6
Described complexing agent is selected from oxolane, 1,3-dioxolane, 1,4-dioxane, methyl ether, ether or propyl ether etc., the mixed solution of described complexing agent can be the mixed solution of complexing agent and water or the mixed solution of complexing agent, water and ethanol (or isopropyl alcohol);
Described carbon carrier is selected from: activated carbon, CNT, carbon molecular sieve or carbon fiber etc.;
Described reductant solution is selected from NaBH
4, formaldehyde, Na
2S
2O
4, sodium formate or hydrazine etc.;
Described certain atmosphere is selected from Ar, H
2, O
2, N
2, atmosphere or vacuum condition such as air.
More optimize and more particularly, the complexing reducing preparation method of highly alloyed Pt based composite metal nanocatalyst, step is as follows:
1, the injection of catalyst precursor: take by weighing a certain amount of carbon carrier (as activated carbon, CNT, carbon molecular sieve, carbon fiber etc.) and add a certain proportion of H
2PtCl
6(or K
2PtCl
6, Na
2PtCl
6) and contain the weak solution of Ru (or other metals such as Ir, Cr), the general control of the addition of noble metal accounts for 5～80% of carbon carrier amount, and wherein Pt accounts for 10～90% (amounts) of total metal content.In said mixture, add complexing agent (oxolane, 1 on this basis, 3-dioxolane, 1,4-dioxane, methyl ether, ether or propyl ether etc.) and the mixed solution or the oxolane (or 1 of water, 3-dioxolane, 1,4-dioxane, methyl ether, ether, propyl ether etc.), the mixed solution of water and ethanol (or isopropyl alcohol), high-speed stirred (or sonic oscillation) 5 minutes～48 hours is so that mix, component A.
2, low temperature liquid phase reduction: the component A that step 1 obtains slowly adds excessive reductant solution (as NaBH under 0～80 ℃ of condition
4, formaldehyde, Na
2S
2O
4, sodium formate or hydrazine etc.) by mechanical agitation (or sonic oscillation) 0.01～8 hour, make slaine and reducing agent that fully reaction take place, thereby the slaine particulate that restores be adsorbed on the carbon carrier, get B component.
3, post processing part: the B component drying that previous step is obtained suddenly washes with water successively except that after desolvating, alcohol is washed repeatedly, and with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate, then at certain atmosphere (Ar, H
2, O
2, N
2, air etc.) or vacuum condition under 40～150 ℃ of dryings, promptly make PtM/C (M=Ru, Ir, the Cr etc.) catalyst of carbon carrier load, wherein the particle size of noble metal is 1.5～3.5nm.
For Pt based composite metal catalyst, have higher alloying level and just mean that also the arrangement of metallic atom in the catalyst is more orderly, the mutual synergy between multi-element metal is just more obvious, and the performance of catalyst also can be improved significantly.But, obtain highly alloyed Pt based composite metal nanocatalyst, general method is to adopt the high-temperature alloy technology, however under hot conditions, the easier reunion of metallic, thus cause catalyst particle size to increase, the active reduction.
The invention has the advantages that:
1, by in the multi-element metal system, adding a kind of complexing agent that can form complex compound with Pt compound and other metallic compounds, by changing its thermodynamic data and then changing its dynamics rate of reduction, thereby Pt and other metals reduce simultaneously, thereby reach the orderly deposition of multi-element metal, improved the alloying level of composition metal on the carbon carrier surface.Find through the X-diffraction analysis: in composite catalyst, atom alloying levels such as ruthenium, iridium, chromium are up to more than 90%; And the equiatomic alloying level of catalyst ruthenium, rhodium, iridium, chromium that general liquid phase reactor obtains only reaches 10%.The typical X x ray diffraction is seen accompanying drawing 1.
2, owing to adopted the low-temperature reduction technology, therefore the composite catalyst that obtains has less metal particle diameter, and X-ray diffraction and transmission electron microscope studies show that: in the catalyst of acquisition, the average grain diameter of catalyst is between 1.5～3.5nm.The typical X x ray diffraction is seen accompanying drawing 1, and typical transmission electron microscope photo is seen accompanying drawing 2.
3, the present invention utilizes the sterically hindered of complexing agent, thereby has effectively stoped the gathering of metallic, and the Pt based composite metal nanocatalyst of acquisition has favorable uniformity and decentralization.Typical transmission electron microscope photo is seen accompanying drawing 2.
4, electrochemical research method such as utilization cyclic voltammetry etc. has been studied the catalytic oxidation of catalyst to methyl alcohol, formic acid, and experimental result is also found: the catalyst that makes shows very excellent electrocatalysis characteristic.Compare with external ETEK company sample, the catalyst that the present invention makes will improve more than 200% the electrocatalytic oxidation property of methyl alcohol (sees accompanying drawing 3).
Description of drawings
Fig. 1 shows that this catalyst has higher alloying level;
Fig. 2 is the TEM photo of PtRu/C catalyst;
Fig. 3 is the PtRu/C catalyst and the cyclic voltammogram of similar Pt-Ru/C catalyst.
The specific embodiment
Embodiment 1:
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.32ml 0.0386mol/L H
2PtCl
6Solution and 0.52ml 0.09635mol/L RuCl
3, adding the mixed solution of oxolane and water subsequently, high-speed stirred 20 hours is so that mix.
2, under 10 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Ru/C catalyst under air conditions, and wherein catalyst particle size is about 1.5～3.5nm.
The metal carrying capacity is 20%, the PtRu atomic ratio is the XRD figure spectrum of 1: 1 self-control PtRu/C catalyst.
Fig. 1 shows that this catalyst has higher alloying level, and in alloy, the atomic fraction of Ru is 46, and the Ru atomic fraction of alloying accounts for 92 of total Ru atom; And do not add in the PtRu/C catalyst of the same type that complexing agent makes, in the alloy, the atomic fraction of Ru only is 10 (being similar to ETEK company sample of the same type), the Ru atomic fraction of alloying accounts for 20 of total Ru atom.Can primary Calculation obtain in the PtRu composition metal nanocatalyst according to the XRD figure spectrum, the average grain diameter of metallic is greatly about 3nm, a little more than the sample of E-TEK company.
Fig. 2 is 20%, the PtRu atomic ratio is the TEM photo of 1: 1 PtRu/C catalyst.Photo clearly demonstrates in the PtRu composite nano-catalyst that makes by the complexing method of reducing, and the average grain diameter of metallic is greatly about 3nm, and metallic has favorable uniformity and decentralization.
Fig. 3 is 20%, the PtRu atomic ratio is that 1: 1 PtRu/C catalyst and business-like E-TEK company similar Pt-Ru/C catalyst is at 0.5mol/L CH
3OH+0.5mol/L H
2SO
4Cyclic voltammogram in the solution.The methanol oxidation peak of just sweeping on the direction at the cyclic voltammetry curve current potential all appears at about 0.47V, but peak current density difference.The peak current density of methyl alcohol oxidation on self-control Pt-Ru/C catalyst and business-like E-TEK company catalyst is respectively 4.25 and 1.96mA/cm
2Compare the sample of E-TEK company, self-control Pt-Ru/C catalyst has improved 2.17 times to the electrocatalytic oxidation property of methyl alcohol.
Embodiment 2:
1, taking by weighing 60mg self-control caliber is 10～20nm CNT, adds 1.32ml 0.0386mol/LH
2PtCl
6Solution and 0.52ml0.09635mol/L RuCl
3, adding the mixed solution of oxolane, water and ethanol subsequently, high-speed stirred 20 hours is so that mix.
2, under 60 ℃, slowly add excessive reductant solution (HCOONa), mechanical agitation 4 hours makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Ru/CNTs catalyst under air conditions, and wherein catalyst particle size is about 1.5-3.5nm.
Embodiment 3:
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.32ml0.0386mol/L H
2PtCl
6Solution and 0.52ml0.09635mol/L OsCl
3, add 1 subsequently, the mixed solution of 4-dioxane and water, high-speed stirred 20 hours is so that mix.
2, under 80 ℃, slowly add excessive reductant solution (Na
2S
2O
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Os/C catalyst under vacuum condition, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 4:
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.32ml0.0386mol/L H
2PtCl
6Solution and 0.52ml0.09635mol/L PdCl
2, add 1 subsequently, the mixed solution of 4-dioxane and water, high-speed stirred 20 hours is so that mix.
2, under 0 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Pd/C catalyst under air conditions, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 5:
1 to take by weighing 60mg self-control caliber be 10～20nm CNT, adds 1.32ml 0.0386mol/LH
2PtCl
6Solution and 0.52ml0.09635mol/L OsCl
3, adding the mixed solution of oxolane, water and ethanol subsequently, high-speed stirred 20 hours is so that mix.
2, under 10 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Os/CNTs catalyst under air conditions, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 6
1, takes by weighing the 60mg carbon molecular sieve, add 1.32ml 0.0386mol/L H
2PtCl
6Solution and 0.52ml0.09635mol/L RuCl
3, add 1 subsequently, the mixed solution of 3-dioxolane, water and ethanol, high-speed stirred 20 hours is so that mix.
2, under 10 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings under air conditions promptly make the Pt-Ru catalyst of carbon molecular sieve load, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 7
1, takes by weighing the 60mg carbon fiber, add 1.32ml 0.0386mol/L H
2PtCl
6Solution and 0.52ml0.09635mol/L IrCl
3, add 1 subsequently, the mixed solution of 3-dioxolane, water and ethanol, high-speed stirred 20 hours is so that mix.
2, under 10 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings under air conditions promptly make carbon fiber loaded Pt-Ir catalyst, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 8
1, takes by weighing the 60mg carbon molecular sieve, add 1.32ml 0.0386mol/L H
2PtCl
6Solution and 0.52ml0.09635mol/L RhCl
3, adding the mixed solution of methyl ether, water and isopropyl alcohol subsequently, high-speed stirred 20 hours is so that mix.
2, add reducing agent under 0 ℃ of condition, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings under air conditions promptly make the Pt-Ru catalyst of carbon molecular sieve load, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 9
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.88ml 0.0386mol/L Na
2PtCl
6Solution and 3.38ml 0.09635mol/L Cr
2(SO
4)
3, adding the mixed solution of the mixed solution of ether and water and isopropyl alcohol subsequently, high-speed stirred 20 hours is so that mix.
2, under 20 ℃, slowly add excessive reductant solution (hydrazine solution), mechanical agitation 2 hours makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.At H
2The following 140 ℃ of dryings of atmospheric condition promptly make the Pt-Cr/C catalyst, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 10
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.88ml 0.0386mol/L H
2PtCl
6Solution and 3.38ml 0.09635mol/L Cr
2(SO
4)
3, adding the mixed solution of the mixed solution of propyl ether and water and isopropyl alcohol subsequently, high-speed stirred 20 hours is so that mix.
2, under 80 ℃, slowly add excessive reductant solution (sodium formate solution), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.At N
2The following 60 ℃ of dryings of atmospheric condition promptly make the Pt-Cr/C catalyst, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 11
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 1.88ml 0.0386mol/L H
2PtCl
6Solution and 3.38ml 0.09635mol/L Cr
2(SO
4)
3, adding the mixed solution of the mixed solution of propyl ether and water and isopropyl alcohol subsequently, high-speed stirred 20 hours is so that mix.
2, under 40 ℃, slowly add excessive reductant solution (hydrazine solution), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Cr/C catalyst under vacuum condition, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 12
1, takes by weighing the Vulcan XC-72R activated carbon powder of 60mg Cabot company, add 0.38ml 0.0386mol/L H
2PtCl
6Solution and 0.02ml 0.09635mol/L RuCl
3, adding the mixed solution of the mixed solution of methyl ether and water and isopropyl alcohol subsequently, high-speed stirred 1 hour is so that mix.
2, under 10 ℃, slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, drying washes with water after removing and desolvating successively, alcohol washes repeatedly, and with the liquor argenti nitratis ophthalmicus check, do not have chlorion in eluate.60 ℃ of dryings promptly make the Pt-Ru/C catalyst under the Ar atmospheric condition, and wherein catalyst particle size is about 1.5～3.5nm.
Embodiment 13, and is basic identical with the foregoing description, but the solution of Pt compound adopts K
2PtCl
6Reductant solution adopts formaldehyde; Dry atmosphere adopts O
2
Claims (2)
1, a kind of complexing reducing preparation method of highly alloyed Pt-based composition metal nanocatalyst, step is as follows:
The injection of catalyst precursor: add Pt compound and other solution of metal compound at carbon carrier, the Pt compound that adds and the amount of other metallic compounds account for 5～80% of carbon carrier, in said mixture, add the complexing agent mixed solution on this basis, stirring makes and mixes, get component A, described other metallic compounds are: a kind of in Ru, Ir or the Cr compound, and wherein the amount of Pt accounts for 10～90% of total metal content;
Low temperature liquid phase reduction: component A slowly adds excessive reductant solution and stirs under 0～80 ℃ of condition, the slaine particulate that restores is adsorbed on the carbon carrier, gets B component;
The post processing part: the B component drying washes with water after removing and desolvating successively, alcohol is washed repeatedly, and 40～150 ℃ of dryings under certain atmosphere then promptly make Pt-Ru/C or the Pt-Cr/C or the Pt-Ir/C catalyst of carbon carrier load,
The solution of described Pt compound is selected from H
2PtCl
6, K
2PtCl
6Or Na
2PtCl
6
Described complexing agent is selected from oxolane, 1,3-dioxolane, 1,4-dioxane, methyl ether, ether or propyl ether; The mixed solution of described complexing agent is the mixed solution of complexing agent and water or the mixed solution of complexing agent, water and ethanol or isopropyl alcohol;
Described carbon carrier is selected from: activated carbon, CNT, carbon molecular sieve or carbon fiber;
Described reductant solution is selected from NaBH
4, formaldehyde, Na
2S
2O
4, sodium formate or hydrazine;
Described certain atmosphere is selected from Ar, H
2, N
2, O
2, air or vacuum atmosphere,
Described highly alloyed being meant: in this composite catalyst, ruthenium, iridium, chromium atom alloying level reach more than 90%.
2, according to the complexing reducing preparation method of the described highly alloyed Pt-based composition metal nanocatalyst of claim 1, it is characterized in that concrete steps are:
The injection of catalyst precursor: take by weighing a certain amount of carbon carrier and add a certain proportion of H
2PtCl
6, K
2PtCl
6Or Na
2PtCl
6With a kind of weak solution that contains in Ru, Ir or the Cr compound, the amount that noble metal adds accounts for 5～80% of carbon carrier amount, wherein the amount of Pt accounts for 10～90% of total metal content, in said mixture, add complexing agent and the mixed solution of water or the mixed solution of complexing agent, water and ethanol or isopropyl alcohol on this basis, high-speed stirred or sonic oscillation 5 minutes～48 hours be so that mix, component A;
The low temperature liquid phase reduction: the component A that step 1 obtains slowly adds excessive reductant solution under 0～80 ℃ of condition, by mechanical agitation or sonic oscillation 0.01～8 hour, make slaine and reducing agent that fully reaction take place, thereby the slaine particulate that restores is adsorbed on the carbon carrier, get B component;
The post processing part: the B component drying that step 2 is obtained washes with water successively except that after desolvating, alcohol is washed repeatedly, and with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate, then at Ar, H
2, N
2, O
2, or the atmosphere of air under, 40～150 ℃ of dryings promptly make the PtM/C catalyst of carbon carrier load, M=Ru, Ir or Cr, wherein the particle size of noble metal is 1.5～3.5nm.
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| CN102847538B (en) * | 2007-07-06 | 2016-07-06 | M技术株式会社 | The manufacture method of the crystallization formed by fullerenes and manufacture device |
| CN102145305A (en) * | 2011-04-08 | 2011-08-10 | 南京航空航天大学 | Method for preparing graphene-loaded nano alloy catalyst |
| CN103840177A (en) * | 2012-11-27 | 2014-06-04 | 李文鹏 | Formic acid fuel cell anode catalytic material |
| CN106563462A (en) * | 2016-10-21 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method and application of cobalt-manganese-based catalyst |
| CN108236950A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the Pd-B/C powder as formaldehyde remover |
| CN107175105B (en) * | 2017-05-18 | 2019-06-21 | 青岛大学 | Graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application |
| CN107335431B (en) * | 2017-06-26 | 2019-09-10 | 南京师范大学 | The preparation method and its resulting materials of a kind of embedded porous Pd/C nanometers of frame and application |
| CN108654701B (en) * | 2018-04-17 | 2020-11-10 | 清华大学 | Method for synthesizing atomic-level dispersion metal oxygen reduction catalyst by solution |
| CN109939675A (en) * | 2019-02-24 | 2019-06-28 | 北京氦舶科技有限责任公司 | A kind of preparation and application of noble metal catalyst |
| CN112002915B (en) * | 2020-07-23 | 2021-07-13 | 北京卫星制造厂有限公司 | Oxygen electrode bifunctional catalyst, preparation method and application |
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| 高活性的Pt-Ru/C抗CO摧化剂. 侯中军等.电源技术，第26卷第4期. 2002 |
| 高活性的Pt-Ru/C抗CO摧化剂. 侯中军等.电源技术，第26卷第4期. 2002 * |
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