CN108232217A - A kind of PtAu/PtMe elctro-catalysts and its preparation and application - Google Patents

A kind of PtAu/PtMe elctro-catalysts and its preparation and application Download PDF

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CN108232217A
CN108232217A CN201611133328.6A CN201611133328A CN108232217A CN 108232217 A CN108232217 A CN 108232217A CN 201611133328 A CN201611133328 A CN 201611133328A CN 108232217 A CN108232217 A CN 108232217A
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ptme
ptau
catalyst
elctro
catalysts
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孙公权
李玉萍
姜鲁华
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention provides a kind of PtAu/PtMe elctro-catalysts and its preparation and application, and Pt forms two kinds of phases of PtAu alloys and PtMe alloys in the PtAu/PtMe elctro-catalysts；The elctro-catalyst PtMe is Pt and the alloys formed one or more kinds of in Fe, Co, Ni；The atomic ratio of Pt and Au is 2:1~8:1.Compared with prior art, without Additional Protection agent and reducing agent in Au reduction processes of the present invention, synthetic route is simple and easy to do, and the resistance to phosphoric acid of gained PtAu/PtMe catalyst poisons and electrochemical cycle stability is good.

Description

A kind of PtAu/PtMe elctro-catalysts and its preparation and application
Technical field
The invention belongs to field of fuel cell technology, more particularly to a kind of using phosphate-doped film as the high temperature of electrolyte Fuel oxygen reduction catalyst.
Background technology
With low temperature (<100 DEG C) Proton Exchange Membrane Fuel Cells compares, high temperature (>100 DEG C) Proton Exchange Membrane Fuel Cells tool There are the raising of the poisonous substances abilities such as electrode reaction kinetic rate fast, elctro-catalyst anti-CO, reactants and products to be gas phase and cause Hydro-thermal manages the advantages such as relatively simple, as green high-efficient power generator, has in fields such as mobile power, portable power stations wide Application prospect [1], cause the extensive interest of researcher in recent years.But high temperature proton exchange film fuel cell is using Some problems are still remained in the process.First, by the research of last decade, it is found that the high temperature membrane of generally use is phosphate-doped and gather Benzimidazole (PBI) has preferable stability and higher proton conductivity under conditions of up to 200 DEG C, but phosphoric acid exists The absorption of Pt bases catalyst surface is strong, causes catalyst poisoning, influences the activity of elctro-catalyst；Simultaneously as operation temperature improves, Under high temperature, strong acid and high condition, Pt base catalyst is more easy to reunite, and stability is challenged by bigger.
In order to overcome the problems referred above, Jong Hyun Jang (ElectrochimicaActa, 2011,56,8802-8810) make For Au@Pt catalyst, the ability that the resistance to phosphoric acid of Pt poisons is improved；Soo-Kil Kim(Applied Catalysis B: Environmental, 2015,165 495-502) find that in acid condition, the absorption of Au surface phosphoric acids is weaker, and then uses CVD method prepares PtAu alloys, reduces phosphoric acid in Pt adsorptions.However, the above method prepares the mistake of Au alloy nano particles Cheng Zhong or the preparation method using complexity --- CVD and electrochemical deposition method are carried in for example above-mentioned document, and using wet-chemical Method (ACS Catal.2016,6,1680-1690；Chem.Sci.,2016,7,3500–3505；Nanoscale,2016,8, 2875-2880) it during the alloy nano particle for preparing Au or Au, then needs additionally to add reducing agent and protective agent, these objects Matter is difficult to thoroughly remove, so as to cause unnecessary pollution to nano-particle.
Invention content
In view of the problems of the existing technology the present invention, has invented a kind of for the phosphate-doped type proton exchange membrane of high temperature PtAu/PtMe elctro-catalysts.The present invention is realized using following technical scheme：
A kind of PtAu/PtMe elctro-catalysts, the active constituent of the elctro-catalyst include Pt, Au and Me, wherein Pt difference Two kinds of alloy phases of PtAu and PtMe are formed with Au and Me, the Me is any one in Fe, Co, Ni or two kinds or more；It is described The atomic ratio of Pt and Au is 2~8 in PtAu/PtMe elctro-catalysts:The atomic ratio of 1, Pt and Me is 1:0.001~1:0.25.
The elctro-catalyst is loaded or non-supported catalyst, the gross mass content of active constituent for 5.6%~ 100%.
The preparation method of the PtAu/PtMe elctro-catalysts, includes the following steps,
1) PtMe catalyst is prepared using ethylene glycol EG reduction methods and/or sodium borohydride reduction or PtMe/C is catalyzed Agent；The atom that PtMe total metal mass content is 5.3%~100%, PtMe in catalyst is 1:0.188~1:1；
2) catalyst obtained by step 1) is added in solvent, ultrasonic disperse forms the first slurries；Catalyst is in solvent Mass concentration 0.5mgCatalyst·ml-1~10mgCatalyst·ml-1；
3) precursor salt of Au is added in into solvent simultaneously stirring and dissolving, a concentration of 0.01mg of AuAu.ml-1~5mgAu.ml-1；
4) precursor salt solution of Au obtained by step 3) is added dropwise and added in into step 2) catalyst slurry, reaction time 2h ~150h, washs, filters, being dried in vacuo loaded or non-supported PtAu/PtMe elctro-catalysts.
Step 2) the solvent is water, ethyl alcohol, methanol, isopropanol, acetone, it is more than one or two kinds of in ether；Step Solvent in rapid 3) described Au precursor salt solutions is water, in ethyl alcohol, methanol, isopropanol, acetone, ether it is one or two kinds of with On.
The precursor salt of Au described in step 3) is HAuCl4、KAuCl4、NaAuCl4In any one；The precursor of the Au A concentration of 0.01mg of Au in salting liquidAu.ml-1~5mgAu.ml-1；When step 2) catalyst slurry is 5-100ml, before reaction The addition rate of body salting liquid is less than 1gAu·min-1。
Step 3) the vacuum drying temperature is 25 DEG C~80 DEG C.
The EG reduction methods add in the ethylene glycol solution pH modulation of NaOH for the precursor salt of Pt and Me are dissolved in ethylene glycol More than 13, it is heated to 150-200 degrees Celsius and keeps the temperature 1-6h；50-100 DEG C is cooled to, is added without or adds in carbon dust and by pH value 5-6 or so is adjusted to, the reaction was continued 0.5-2h, washing, filtering, vacuum drying；
The sodium borohydride reduction is that Pt and Me precursor salts and CTAB are dissolved in deionized water, is added without or adds in carbon Powder is stirred and heated to 60-80 DEG C, by NaBH4And NaOH is dissolved in deionized water, and is added dropwise to the precursor salt solution of aforementioned Pt In, and 0.5~4h is reacted, solid is centrifugally separating to obtain, cleans and is dried in vacuo repeatedly with hot water.
Pt precursor salts are H2PtCl6, Na2PtCl6, K2PtCl6, Na2PtCl4, K2PtCl4；Me precursor salts are Fe, Co, Ni Chloride, nitrate, sulfate or acetate.
The PtAu/PtMe elctro-catalysts are high temperature proton exchange film fuel cell oxygen reduction catalyst.
Dielectric film in the high temperature proton exchange film fuel cell is phosphate-doped proton exchange membrane.
Compared with prior art, the present invention has the following advantages：
The resistance to phosphoric acid of 1.PtAu/PtMe catalyst is functional, compared with PtMe, has higher ORR in phosphoric acid electrolyte Activity；
2.PtAu/PtMe catalyst, which is applied to high temperature phosphoric acid fuel cell, has good electrochemical cycle stability；
3. in preparation process, without additionally adding reducing agent, protective agent need not be added, without after additional in Au reduction processes Processing.
Description of the drawings
Fig. 1 is the XRD diffracting spectrums of five gained PtNi/PtAu/C of embodiment, and ranging from 10 °~90 ° of twice of angle of diffraction is swept Speed is retouched as 5 °/min, step-length is 0.02 °.
The half-cell characterization gained polarization curves of oxygen reduction that Fig. 2 is five gained PtAu/PtNi/C of embodiment, sweep speed are 10mV.s-1, electrolyte is 0.1M HClO4、0.1M HClO4With 0.1M H3PO4Mixed solution, rotating disk electrode (r.d.e) rotating speed are 1600rpm。
Fig. 3 is the XRD diffracting spectrums of one gained PtAu/PtCo/C-2 of comparative example and PtAu/PtCo/C obtained by example IV, Ranging from 10 °~90 ° of twice of angle of diffraction, sweep speed are 5 °/min, and step-length is 0.02 °.
Specific embodiment
Embodiment one
By 10.5mg H2PtCl6And 0.57mg FeCl3Be dissolved in 20ml ethylene glycol, add in 10ml1mol.L-1NaOH Ethylene glycol solution, be heated to 150 degrees Celsius and keep the temperature 6hour；It is cooled to 50 degrees Celsius, adds in 94.7mg carbon dusts and by pH value 5-6 or so is adjusted to, the reaction was continued 0.5h, washing, filtering, vacuum drying；Total metal mass, which accounts for, in gained PtFe/C catalyst urges The molar ratio of 5.3%, the Pt and Fe of agent are 1:0.188.The above-mentioned PtFe/C catalyst powders of above-mentioned 50mg are taken, 5ml is added in and goes Ionized water and 95ml alcohol mixeding liquids, ultrasonic disperse is into homogeneous slurry, a concentration of 0.5mg.ml of catalyst quality-1.Take 0.545mg HAuCl4, simultaneously ultrasonic disperse is uniform for the mixed liquor dilution of addition 40ml water and 14ml ethyl alcohol, and the mass concentration of Au is 0.01mgAu.ml-1.By HAuCl4Solution is added dropwise to peristaltic pump in PtFe/C catalyst slurries, rate of addition 0.01mgAu.min-1), continuing stirring makes reaction 1.5h.Slurries are filtered, washed after reaction, 75 degrees Celsius of lower vacuum are done It is dry.Catalyst is denoted as PtAu/PtFe/C, and the atomic ratio that wherein total metal mass accounts for 5.6%, the Pt and Au of catalyst is 2:1.It will It is applied in high temperature proton exchange film fuel cell ORR reactions, and compared with PtFe/C, resistance to phosphoric acid poisons ability and significantly carries It is high.
Embodiment two
By 196.4mg Na2PtCl4And 80.5mg Co (C2H3O2)2Precursor salt is dissolved in CTAB in deionized water, and stirring is simultaneously 60 DEG C are heated to, by 40mg NaBH4And 40mg NaOH are dissolved in deionized water, and are added dropwise to the precursor salt solution of aforementioned Pt In, and 4h is reacted, solid is centrifugally separating to obtain, cleans and is dried in vacuo repeatedly with hot water.Metal is total in gained PtCo catalyst The molar ratio that quality accounts for 100%, the Pt and Co of catalyst quality is 1:1.Above-mentioned 50mg PtCo catalyst powders are taken, add in 4ml Simultaneously ultrasonic disperse is uniform for deionized water and 1ml methyl alcohol mixed liquors, a concentration of 10mg.ml of catalyst quality-1.It takes 36.84mgKAuCl4, add in 3ml deionized waters and 0.84ml methyl alcohol mixed liquors and ultrasonic disperse.By KAuCl4Aqueous solution is to wriggle Pump is added dropwise in PtCo catalyst slurries, and 39min (rate of addition 0.5mg are added dropwise altogetherAu.min-1), continue to be stirred to react 3h.Slurries are filtered after reaction, are washed with deionized, are dried in vacuo under 25 degrees Celsius of room temperature.Catalyst is denoted as PtAu/ The atomic ratio that PtCo, wherein total metal mass account for 100%, the Pt and Au of catalyst is 2:1.It is applied to high temperature proton exchange In the ORR reactions of membrane cell, compared with PtCo, electrochemical cycle stability improves.
Embodiment three
By 212.8mg K2PtCl4And 79.5mg NiSO4Precursor salt is dissolved in CTAB in deionized water, is stirred and heated to 80 DEG C, by 40mg NaBH4And 40mg NaOH are dissolved in deionized water, and are added dropwise in the precursor salt solution of aforementioned Pt, and anti- 0.5h is answered, is centrifugally separating to obtain solid, cleans and is dried in vacuo repeatedly with hot water.(total metal mass accounts for gained PtNi catalyst The molar ratio of 100%, the Pt and Ni of catalyst quality are 1:1).The above-mentioned PtNi catalyst powders of 50mg are taken, add in 1ml deionizations Water and 4ml methanol mixed solution and ultrasonic disperse are into homogeneous slurry, a concentration of 10mg.ml of catalyst quality-1.Take 35.63 mg NaAuCl4Aqueous solution, adds in 10ml deionized waters and 90ml methyl alcohol mixed liquors and ultrasonic disperse is uniform.By KAuCl4Aqueous solution with Peristaltic pump is added dropwise in PtNi catalyst slurries, and 39min (rate of addition 0.5mg are added dropwise altogetherAu.min-1), it is anti-to continue stirring Answer 2h.Slurries are filtered after reaction, are washed with deionized, are dried in vacuo under 25 degrees Celsius of room temperature.Catalyst is denoted as The atomic ratio that PtAu/PtNi, wherein total metal mass account for 100%, the Pt and Au of catalyst is 2:1.It is applied to high temperature matter In the ORR reactions of proton exchange film fuel cell, compared with PtNi, resistance to phosphoric acid poisons ability and significantly improves.
Example IV
By 46.6mg Na2PtCl6And 13.3mg CoCl2Be dissolved in 20ml ethylene glycol, add in 15ml 1mol.L-1's The ethylene glycol solution of NaOH is heated to 200 degrees Celsius and keeps the temperature 1hour；100 degrees Celsius are cooled to, addition 74mg carbon dusts simultaneously will PH value is adjusted to 6 or so, the reaction was continued 2h, washing, filtering, vacuum drying；Gained PtCo/C catalyst metals gross masses account for catalysis The molar ratio of 26%, the Pt and Co of agent quality are 1:1.Above-mentioned 50mg PtCo/C catalyst powders are taken, add in 47ml deionized waters And 3ml isopropanol mixed liquors, ultrasonic disperse is into homogeneous slurry.Take 8.717mg HAuCl4, add in 49ml deionized waters and 1ml be different Propyl alcohol mixed liquor, ultrasonic disperse is into solution.By HAuCl4Solution is added dropwise to PtCo/C catalysts agent slurry with peristaltic pump In liquid, 60min (rate of addition 0.084mg are added dropwise altogetherAu.min-1), continue to be stirred to react 2h.Slurries are filtered after reaction, It is washed with a certain amount of deionized water, is dried in vacuo under 25 degrees Celsius of room temperature.Catalyst is denoted as PtAu/PtCo/C, and wherein metal is total The atomic ratio that quality accounts for 30%, the Pt and Au of catalyst is 2:1.PtAu monocrystalline grain size is 2.3nm, PtCo in PtAu/PtCo/C Monocrystalline grain size is 2.1nm.It is applied in the ORR reactions of high temperature proton exchange film fuel cell, compared with PtCo, electrification Cyclical stability is learned to improve.
Embodiment five
By 49.9mg K2PtCl6And 18.8mg Ni (NO3)2Be dissolved in 20ml ethylene glycol, add in 20ml 1mol.L-1's PH value is modulated more than 14, is heated to 180 degrees Celsius and keeps the temperature 3hour by the ethylene glycol solution of NaOH；80 degrees Celsius are cooled to, It adds in 74mg carbon dusts and pH value is adjusted to 6 or so, the reaction was continued 1.5h, washing, filtering, vacuum drying；Gained 20%PtNi/C The molar ratio that total metal mass accounts for 26%, the Pt and Ni of catalyst quality in catalyst is 1:1.The above-mentioned PtNi/C of 100mg is taken to urge Agent, adds in 49ml deionized waters and 1ml acetone, and ultrasonic disperse is into homogeneous slurry, a concentration of 2mg.mL of catalyst quality-1.It takes 8.717mg HAuCl4, add in 48ml deionized waters and 2ml acetone and ultrasonic dissolution.By HAuCl4Solution is added dropwise to PtNi/ In C catalyst slurries, 120min, rate of addition 0.04mg are added dropwise altogetherAu.min-1, and continue to stir and continue reaction 24h.Slurries are filtered after reaction, are washed with deionized, are dried in vacuo under 25 degrees Celsius, obtain catalyst Pt Au/PtNi/ The atomic ratio that C, wherein total metal mass account for 30%, the Pt and Au of catalyst is 2:1.It is applied to high temperature proton exchange film combustion In the ORR reactions for expecting battery, compared with PtNi/C, resistance to phosphoric acid poisons ability and significantly improves.
Attached drawing 1 is the XRD diffracting spectrums of five gained PtNi/PtAu/C of embodiment, by can be seen that in PtNi/PtAu/C in figure Metallic element forms two kinds of crystalline phases, is marked out respectively with five-pointed star ★ and ■.Wherein, with five-pointed star ★ mark diffraction peak in It is PtAu alloy phases between Pt and the diffraction maximum of Au；And it is then between Pt and the diffraction maximum of Ni with the diffraction maximum of ■ marks PtNi alloy phases.And the grain size of catalyst can be acquired by Scherrer formula, wherein PtNi monocrystalline grain size and PtAu monocrystalline grain sizes Respectively less than 3nm.
(electrolyte is 0.1M HClO to the half-cell characterization result that attached drawing 2 is five gained PtAu/PtNi/C of embodiment4And 0.1M HClO4+0.1M H3PO4, sweep speed 10mV.s-1, electrode rotating speed is 1600rpm) and straight line is 0.1M HClO4Middle survey Test result, scatterplot are then 0.1M HClO4+0.1M H3PO4Middle test result.During the test, added by Tu Ke get, PtNi/C Enter H3PO4Afterwards, ORR curves half wave potential is down to 0.836 volt by 0.908 volt, and fall is 72 millivolts；And PtAu/PtNi/C After phosphoric acid is added in, ORR curves half wave potential is down to 0.838 by 0.880 volt, only declines 52 millivolts.Illustrate that PtAu/PtNi/C is resistance to The ability that phosphoric acid poisons improves a lot compared with PtNi/C.
Embodiment six
By 49.9mg K2PtCl6And 5.36mg Ni (C2H3O2)2Be dissolved in 20ml ethylene glycol, add in 20ml 1mol.L-1 NaOH ethylene glycol solution, by pH value modulate more than 14, be heated to 180 degrees Celsius and keep the temperature 3hour；It is Celsius to be cooled to 80 Degree adds in 78mg carbon dusts and pH value is adjusted to 6 or so, the reaction was continued 2h, washing, filtering, vacuum drying；Gained PtNi/C is catalyzed (molar ratio that total metal mass accounts for 22%, the Pt and Ni of catalyst quality is 3 for agent:1).The above-mentioned PtNi/C powders of 50mg are taken, are added Enter 49ml deionized waters and 1ml ether mixed liquors, ultrasonic disperse is into homogeneous slurry, a concentration of 1mg.mL of catalyst quality-1.It takes 2.179mg HAuCl4, it is uniform to add in mixed liquor dilution and ultrasonic disperse of the 45ml water with 5ml ether.By HAuCl4Aqueous solution with Peristaltic pump is added dropwise to Pt3In Ni catalyst slurries, 30min (rate of addition 0.042mg are added dropwise altogetherAu.min-1), continue to stir Make reaction uniformly and continue stirring for 24 hours, ensure that the reaction was complete by Au.Slurries are filtered after reaction, are washed with deionized, and It is dried in vacuo under 25 degrees Celsius of room temperature.Catalyst is denoted as PtAu/PtNi/C-2, and wherein total metal mass accounts for catalyst The atomic ratio of 24%, Pt and Au are 8:1.It is applied in the ORR reactions of high temperature proton exchange film fuel cell, electrochemistry Cyclical stability is preferable.
Comparative example one
By 46.6mg Na2PtCl6And 13.3mg CoCl2Be dissolved in 20ml ethylene glycol, add in 15ml 1mol.L-1's The ethylene glycol solution of NaOH is heated to 200 degrees Celsius and keeps the temperature 1hour；100 degrees Celsius are cooled to, addition 74mg carbon dusts simultaneously will PH value is adjusted to 6 or so, the reaction was continued 2h, washing, filtering, vacuum drying；Gained PtCo/C catalyst metals gross masses account for catalysis The molar ratio of 26%, the Pt and Co of agent quality are 1:1.Above-mentioned 50mg PtCo/C catalyst powders are taken, add in 47ml deionized waters And 3ml isopropanol mixed liquors, ultrasonic disperse is into homogeneous slurry.Take 8.717mg HAuCl4, add in 49ml deionized waters and 1ml be different Propyl alcohol mixed liquor, ultrasonic disperse is into solution.By HAuCl4Solution is toppled over rapidly in addition to PtCo/C catalyst agent slurries, Continue to be stirred to react 2h.Slurries are filtered after reaction, are washed with a certain amount of deionized water, 25 degrees Celsius of lower vacuum of room temperature are done It is dry.Catalyst is denoted as PtAu/PtCo/C-2, and the atomic ratio that wherein total metal mass accounts for 30%, the Pt and Au of catalyst is 2:1. Au does not form alloy with Pt in gained PtAu/PtCo/C-2, and monocrystalline grain size is more than 10nm, is applied to high temperature proton exchange In the ORR reactions of membrane cell, compared with PtAu/PtCo/C in example IV, ORR activity is poor.
XRD diffraction pattern of the attached drawing 3 for PtAu/PtCo/C in one gained PtAu/PtCo/C-2 of comparative example and example IV Spectrum, by can be seen that in figure, metallic element forms two kinds of crystalline phases in PtAu/PtCo/C obtained by example IV, respectively with five-pointed star ★ and ■ is marked out.Wherein, it is PtAu alloys with the diffraction peak of five-pointed star ★ marks between Au and the diffraction maximum of Pt, and with mark The diffraction maximum of note is then PtCo alloy phases between Pt and the diffraction maximum of Co.And only containing PtCo alloys, Au in comparative example one It is then pure phase, is marked with ▼, do not generate alloy.Gained and the grain size that catalyst can be acquired by Scherrer formula, wherein PtCo Monocrystalline grain size is 2.0nm, and Au monocrystalline grain size is then more than 8nm, illustrates that group occurs for Au in one gained PtAu/PtCo/C-2 of comparative example It is poly-.

Claims (10)

1. a kind of PtAu/PtMe elctro-catalysts, it is characterised in that：The active constituent of the elctro-catalyst includes Pt, Au and Me, Middle Pt forms two kinds of alloy phases of PtAu and PtMe with Au and Me respectively, the Me be any one in Fe, Co, Ni or two kinds with On；The atomic ratio of Pt and Au is 2~8 in the PtAu/PtMe elctro-catalysts:The atomic ratio of 1, Pt and Me is 1:0.001~1: 0.25。
2. loaded or non-supported PtAu/PtMe elctro-catalysts as described in claim 1, it is characterised in that：The electro-catalysis Agent is loaded or non-supported catalyst, and the gross mass content of active constituent is 5.6%~100%.
3. the preparation method of PtAu/PtMe elctro-catalysts as described in claim 1-2 is any, it is characterised in that：Including following step Suddenly,
1) PtMe catalyst or PtMe/C catalyst are prepared using ethylene glycol EG reduction methods and/or sodium borohydride reduction；It urges The atom that PtMe total metal mass content is 5.3%~100%, PtMe in agent is 1:0.188~1:1；
2) catalyst obtained by step 1) is added in solvent, ultrasonic disperse forms the first slurries；Quality of the catalyst in solvent Concentration 0.5mgCatalyst·ml-1~10mgCatalyst·ml-1；
3) precursor salt of Au is added in into solvent simultaneously stirring and dissolving, a concentration of 0.01mg of AuAu.ml-1~5mgAu.ml-1；
4) precursor salt solution of Au obtained by step 3) is added dropwise and added in into step 2) catalyst slurry, the reaction time for 2h~ 150h, washs, filters, being dried in vacuo loaded or non-supported PtAu/PtMe elctro-catalysts.
4. the preparation method of load PtAu/PtMe elctro-catalysts as claimed in claim 3, it is characterised in that：Step 2) the solvent To be more than one or two kinds of in water, ethyl alcohol, methanol, isopropanol, acetone, ether；In step 3) the Au precursor salt solutions Solvent be water, ethyl alcohol, methanol, isopropanol, acetone, it is more than one or two kinds of in ether.
5. the preparation method of PtAu/PtMe elctro-catalysts as claimed in claim 3, it is characterised in that：Au described in step 3) Precursor salt is HAuCl4、KAuCl4、NaAuCl4In any one；Au's is a concentration of in the precursor salt solution of the Au 0.01mgAu.ml-1~5mgAu.ml-1；When step 2) catalyst slurry is 5-100ml, the addition rate of reacting precursor salting liquid Less than 1gAu·min-1。
6. the preparation method of PtAu/PtMe elctro-catalysts as claimed in claim 3, it is characterised in that：Step 3) the vacuum is done Dry temperature is 25 DEG C~80 DEG C.
7. the preparation method of PtAu/PtMe elctro-catalysts as claimed in claim 3, it is characterised in that：
The EG reduction methods for the precursor salt of Pt and Me are dissolved in ethylene glycol, add in the ethylene glycol solution pH modulation 13 of NaOH with On, it is heated to 150-200 degrees Celsius and keeps the temperature 1-6h；50-100 DEG C is cooled to, be added without or add in carbon dust and is adjusted to pH value 5-6 or so, the reaction was continued 0.5-2h, washing, filtering, vacuum drying；
The sodium borohydride reduction is that Pt and Me precursor salts and CTAB are dissolved in deionized water, is added without or adds in carbon dust, 60-80 DEG C is stirred and heated to, by NaBH4And NaOH is dissolved in deionized water, and is added dropwise in the precursor salt solution of aforementioned Pt, And 0.5~4h is reacted, solid is centrifugally separating to obtain, cleans and is dried in vacuo repeatedly with hot water.
8. the preparation method of PtAu/PtMe elctro-catalysts as claimed in claim 7, it is characterised in that：Pt precursor salts are H2PtCl6, Na2PtCl6, K2PtCl6, Na2PtCl4, K2PtCl4；Me precursor salts are chloride, nitrate, sulfate or the vinegar of Fe, Co, Ni Hydrochlorate.
9. a kind of application of any PtAu/PtMe elctro-catalysts of claim 1-2, it is characterised in that：The catalyst is High temperature proton exchange film fuel cell oxygen reduction catalyst.
10. the application of PtAu/PtMe elctro-catalysts as claimed in claim 9, it is characterised in that：The high temperature proton exchange film combustion It is phosphate-doped proton exchange membrane to expect the dielectric film in battery.
CN201611133328.6A 2016-12-10 2016-12-10 A kind of PtAu/PtMe elctro-catalysts and its preparation and application Pending CN108232217A (en)

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Application publication date: 20180629