CN103165914A - Pt/Au/PdCo/C catalyst, and preparation and application thereof - Google Patents

Pt/Au/PdCo/C catalyst, and preparation and application thereof Download PDF

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CN103165914A
CN103165914A CN2011104214699A CN201110421469A CN103165914A CN 103165914 A CN103165914 A CN 103165914A CN 2011104214699 A CN2011104214699 A CN 2011104214699A CN 201110421469 A CN201110421469 A CN 201110421469A CN 103165914 A CN103165914 A CN 103165914A
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catalyst
pdco
electrode
preparation
deionized water
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CN103165914B (en
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孙公权
唐琪雯
姜鲁华
姜黔
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Dalian Institute of Chemical Physics of CAS
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    • 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
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Abstract

The invention provides a Pt/Au/PdCo/C catalyst. Preparation of the catalyst comprises the following two steps: (1) preparation of alloyed PdCo/C; and (2) preparation of the Pt/Au/PdCo/C catalyst. The catalyst has the advantages of low Pt load, high electrochemical stability and the like and can be used as a cathodic oxygen reduction catalyst of a metal-air fuel cell, a proton exchange membrane fuel cell and a direct liquid fuel cell.

Description

A kind of Pt/Au/PdCo/C catalyst and preparation and application
Technical field
The present invention relates to a kind of oxygen reduction catalyst, relate to specifically a kind of preparation and application for metal air fuel cell oxygen reduction catalyst, Proton Exchange Membrane Fuel Cells oxygen reduction catalyst, direct liquid fuel battery oxygen reduction catalyst.
Background technology
Along with the consumption of the fuel such as coal, oil and natural gas is day by day exhausted with the reserves of day sharp increase and energy resources, the energy technology of seeking the environmental friendliness sustainable development is extremely urgent.Fuel cell has the advantages such as energy conversion efficiency is high, pollution-free, noiselessness because of it, become the focus of countries in the world research.
At present, the most effective catalyst of fuel battery negative pole ORR catalyst remains Pt and alloy catalyst thereof.And limited reserves and the fancy price of Pt becomes one of business-like obstacle of fuel cell.How to improve its utilance and become recent study hotspot under the prerequisite that does not reduce catalyst activity.
Adzic seminar finds to form individual layer Cu atom by Cu-UPD on the noble metal surface, then with Pt 2+Replace and obtain the Pt single-layer catalyst, wherein kernel generally adopts noble metal and the alloys thereof such as Pd, Au.The Pt of high degree of dispersion makes the ORR specific mass activity of such catalyst greatly improve.Yet, less in the research of electrochemical environment stability inferior for such catalyst.
The Pt/PdCo/C catalyst is carried out accelerated aging test, in the potential range of 0.6-1.0V vs.NHE with 100mV s -1The speed of sweeping carry out CV scanning, after the 10k circle, the half wave potential of ORR polarization curve is negative moves 34mV, catalytic activity obviously decays, and illustrates at the Pt of catalyst surface high degree of dispersion individual layer electrochemical stability relatively poor.The Au nano particle has good electrochemical stability, is introduced into the stability that can improve widely eelctro-catalyst in eelctro-catalyst.Yet the ORR catalytic activity of Au itself is relatively poor, if covered the reduction that the active sites of Pt may cause catalytic activity when being introduced in catalyst.For this reason, the method that our design replace by Cu-UPD-is incorporated into Au between surperficial Pt layer and PdCo core as inferior individual layer, is intended to not reduce the electrochemical stability of raising Pt single-layer catalyst under the prerequisite of ORR catalytic activity.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to provide a kind of preparation and application for metal air fuel cell oxygen reduction catalyst, Proton Exchange Membrane Fuel Cells oxygen reduction catalyst, direct liquid fuel battery oxygen reduction catalyst.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of Pt/Au/PdCo/C catalyst, Pt distributes in nanoparticle surface, and Au is between Pt shell and PdCo core.In catalyst, metal quality accounts for the 12-46% of gross mass; Wherein the mol ratio of Pd and Co is 5: 1-1: 1; The mol ratio of Pd and Au is 5: 1-12: 1; The mol ratio of Pd and Pt is 10: 1-20: 1.
The preparation method of described catalyst comprises the following steps,
(1) preparation of alloying PdCo/C
A. add PdCl in deionized water 2And/or Pd (NO 3) 2, add simultaneously Co (NO 3) 2, CoCl 2, CoBr 2, CoSO 4, Co (COOH) 2In one or more, form mixture, stir and make it to mix, add afterwards carbon carrier in mixed liquor, and ultrasonic to be dispersed to mixed liquor even;
B. drip sodium citrate aqueous solution in above-mentioned steps (1) a gained mixed liquor, and dropwise drip NaBH under the condition of rapid stirring 4The aqueous solution filters to get solid matter after standing, adopts afterwards deionized water that the gained solid matter is washed, and after washing the gained material to be placed in vacuum drying oven dry, get PdCo/C;
C. step (1) b gained PdCo/C is heat-treated in hydrogen and inert gas gaseous mixture, get alloying PdCo/C;
(2) preparation of Pt/Au/PdCo/C catalyst
A. in ethanol, add above-mentioned steps (1) c gained alloying PdCo/C, stir and to add the Nafion emulsion after making it to mix, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (2) a gained mixed liquor, and be coated on the glass-carbon electrode surface as work electrode, electrode and reference electrode are respectively Pt silk and saturated calomel electrode;
C. above-mentioned steps (2) b gained work electrode is placed in H 2SO 4And CuSO 4Keep 1-300s in mixed solution and under the sedimentation potential of 350-520mV, then fast electrode is immersed H 2SO 4And HAuCl 4In mixed solution and standing 1-10min carry out displacement reaction, then with deionized water, that electrode clean is clean;
D. above-mentioned steps (2) c gained work electrode is placed in H 2SO 4And CuSO 4Keep 1-300s in mixed solution under the sedimentation potential of 350-520mV, then fast electrode is immersed H 2SO 4And K 2PtCl 4In mixed solution and standing 1-10min carry out displacement reaction, then with deionized water, that electrode clean is clean, namely obtain the Pt/Au/PdCo/C catalyst.
Pd in mixture described in step (1) a 2+And Co 2+Mol ratio be 5: 1-1: 1; Pd in described mixture 2+Concentration be 10-100mmol L -1
Metal quality described in step (1) in alloying PdCo/C accounts for the 10-40% of gross mass.
Described in step (1) b, the concentration of sodium citrate aqueous solution is 10-50mmol L -1, consumption is 10-50mL; Described NaBH 4The concentration of the aqueous solution is 10-100mmol L -1, consumption is 10-50mL; The described vacuumize time is 5-20 hour.
Inert atmosphere described in step (1) c is one or more the mixture in argon gas, helium, nitrogen; Described hydrogen volume accounts for the 1-10% of volume of gas; Described heat treatment temperature is 200-600 ℃, and described heat treatment time is 1-3 hour;
Described in step (2) a, the concentration of PdCo/C in ethanol is 0.5-5mg mL -1The mass ratio of described Nafion and PdCo/C is 1: 10-1: 1.
H described in step (2) c and step (2) d 2SO 4And CuSO 4In mixed solution, both amount ratio is 5: 1-1: 2; Described H 2SO 4And HAuCl 4In mixed solution, both amount ratio is 100: 1-20: 1; Described H 2SO 4And K 2PtCl 4In mixed solution, both amount ratio is 100: 1-20: 1; Described H 2SO 4Amount concentration be 20-100mmol L -1
Described carbon carrier is: the mixture of one or more in XC-72R, BP2000, acetylene black, carbon nano-tube, graphite;
Described Pt/Au/PdCo/C catalyst can be used as metal air fuel cell oxygen reduction catalyst, Proton Exchange Membrane Fuel Cells oxygen reduction catalyst, direct liquid fuel battery oxygen reduction catalyst.
Compared with prior art, novel Pt/Au/PdCo/C catalyst of the present invention has the following advantages:
1. precious metals pt distributes in nanoparticle surface, has reduced the carrying capacity of Pt, thereby has reduced the cost of catalyst
2. the Au that will have the good electrical chemical stability is incorporated between Pt shell and PdCo core, has greatly improved ORR activity and the electrochemical stability of Pt single-layer catalyst.
Description of drawings
Fig. 1 is at the stripping curve of the Cu of different undercurrent potential deposit (according to embodiment 1-5);
Fig. 2 is the stripping curve (according to embodiment 3 and 6-8) of the Cu of process different time underpotential deposition;
Fig. 3 for the sample for preparing according to embodiment 1 and comparative example 3 at 0.1M HClO 4Cyclic voltammetric in solution (CV) curve and oxygen reduction reaction (ORR) polarization curve;
Fig. 4 for the sample for preparing according to embodiment 1 and comparative example 3 at 0.1M HClO 4CV curve and ORR polarization curve in solution before and after stability test;
Fig. 5 for the sample for preparing according to embodiment 1 and comparative example 3 at 0.1M HClO 4TEM photo in solution before and after stability test;
Fig. 6 for the sample for preparing according to embodiment 1 and comparative example 2 at 0.1M HClO 4TEM photo in solution before and after stability test.
Embodiment:
Below in conjunction with embodiment, the present invention is explained in detail.Certainly the present invention is not limited in these specific embodiments.
Embodiment 1:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 120s in the sedimentation potential of 350mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmolL -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode surface is cleaned up.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Embodiment 2:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 120s in the sedimentation potential of 370mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmolL -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode surface is cleaned up.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Embodiment 3:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 120s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmolL -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then deionized water cleans up electrode surface.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then deionized water totally can obtain the Pt/Au/PdCo/C catalyst with electrode clean.
Embodiment 4:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in solution: at first keep 120s in the sedimentation potential of 420mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmol L -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode surface is cleaned up.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Embodiment 5:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 120s in the sedimentation potential of 520mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmolL -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode surface is cleaned up.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Embodiment 6:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 1s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmol L -1H 2SO 4With 1mmol L -1HAuCl 4In solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then deionized water cleans up electrode surface.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then deionized water totally can obtain the Pt/Au/PdCo/C catalyst with electrode clean.
Embodiment 7:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out the Cu underpotential deposition in mixed solution: at first keep 40s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mmol L -1H 2SO 4With 1mmol L -1HAuCl 4In solution, standing 4min makes Au 3+With Cu 2+Displacement reaction occurs, and then deionized water cleans up electrode surface.Repeat the underpotential deposition of Cu, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min makes Pt 2+With Cu 2+Displacement reaction occurs, and then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Embodiment 8:
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.With the PdCo/C catalyst in 400 ℃, 5vol%H 2Under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying.
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out Cu-UPD in mixed solution: at first keep 300s in the sedimentation potential of 390mV and carry out CU-UPD, then fast electrode is immersed 50mmol L -1H 2SO 4With 1mmol L -1HAuCl 4In mixed solution, standing 4min carries out fully displacement reaction, then with deionized water, that electrode clean is clean.Repeat the Cu-UPD process, then electrode is placed in 50mmol L fast -1H 2SO 4And 1mmolL -1K 2PtCl 4In mixed solution, standing 4min carries out fully displacement reaction, then with deionized water, electrode clean totally can be obtained the Pt/Au/PdCo/C catalyst.
Comparative example 1: the PdCo/C catalyst of alloying
Take 28.2mg PdCl 2With 9.6mg Co (NO 3) 2(the Pd/Co atomic ratio is 3: 1) is dissolved in the 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic dispersion 30min.Wait the rear dropping 25mmol L that is uniformly dispersed -1Then sodium citrate aqueous solution 25mL slowly drips 80mmol L under rapid stirring -1NaBH 4Solution 25mL.After 30min, the product that obtains is filtered, a large amount of deionized water washings, 80 ℃ of dry 8h of vacuum drying oven obtain the PdCo/C catalyst.
The PdCo/C catalyst is heat-treated (400 ℃, 5vol%H 2/ Ar, 2h) can obtain the PdCo/C catalyst of alloying.
Comparative example 2:Pt/PdCo/C catalyst
The PdCo/C catalyst of 5mg alloying is scattered in 2mL ethanol, adds 30 μ L 5%Nafion emulsions to make binding agent.Pipette 20 μ L slurries after ultrasonic dispersion 15min and be coated on the glass-carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1H 2SO 4With 50mmol L -1CuSO 4Carry out Cu-UPD in solution: at first keep 120s in the sedimentation potential of 390mV and carry out Cu-UPD, then electrode is placed in 50mmol L fast -1H 2SO 4With 1mmol L -1K 2PtCl 4In mixed solution, standing 4min carries out fully displacement reaction, then with deionized water, electrode clean totally can be obtained the Pt/PdCo/C catalyst.
Comparative example 3:Pt/C catalyst
Commodity 20wt.%Pt/C catalyst (E-TEK company).
Fig. 1 is at different sedimentation potential deposit 120s, then with 20mV s -1The Cu stripping curve that obtains from this electric potential scanning to 820mV of sweep speed, selected current potential is all higher than the body phase sedimentation potential 340mV of Cu.As seen from Figure 1, along with the negative of sedimentation potential moves, the oxidation peak that is positioned at 470mV and 580mV increases gradually, begins to occur when sedimentation potential is negative the oxidation peak that body deposits Cu mutually when moving to 380mV, illustrate Cu under this current potential artificial body for generating deposit mutually, so sedimentation potential is chosen as 390mV.
Fig. 2 is take 390mV as sedimentation potential, through after different sedimentation times with 20mV s -1Sweep speed scan from 390mV the Cu stripping curve that 820mV obtains.As seen from Figure 2, along with the prolongation of sedimentation time, the Anodic Stripping peak of Cu increases gradually, and stripping curve overlaps substantially after the 120s, the underpotential deposition that Cu is described is saturated, on the PdCo surface, underpotential deposition occurs along with the further prolongation of sedimentation time no longer includes Cu.The phenomenon that in the UPD process, this oneself stops comes from the strong interaction between Cu and precious metals pd, and after the Pd particle surface was wrapped up fully by the Cu individual layer, Cu can't stop at Cu atomic surface generation underpotential deposition.
Fig. 3 for the sample for preparing according to embodiment 1 and comparative example 2 at 0.1M HClO 4CV curve in solution and ORR polarization curve.Can be found out by Fig. 3 (a), compare with the Pt/PdCo/C catalyst, the hydrogen adsorption desorption peak of Pt/Au/PdCo/C decreases, and the electro-chemical activity surface area (ECSAs) that calculates by integration hydrogen desorption peak is respectively 149.3 and 144.3m 2g -1, so high ECSAs may cause in the catalyst surface high degree of dispersion due to Pt.Simultaneously in the Pt/Au/PdCo/C catalyst, the redox peak of Pt when high potential all decreases and moves to high potential, illustrate that OH is easier of Pt surface generation adsorption desorption, indicating that the ORR catalytic activity will increase.By Fig. 3 (b) as can be known, introduce the ORR catalytic activity that Au has improved catalyst between Pt and PdCo, the half wave potential of ORR polarization curve is just moving to 0.90V by 0.878V, has improved 22mV.
Fig. 4 be embodiment 1 and comparative example 2,3 (0.85V and 0.9V) unit mass Pt under certain potentials the dynamics current ratio.Compare with the Pt/PdCo/C catalyst with Pt/C, Pt/Au/PdCo/C catalyst ORR catalytic activity when 0.85V has improved respectively 13 and 4 times, has greatly improved the utilance of precious metals pt.The raising of ORR catalytic activity may be owing to causing the Pt Lattice Contraction adding of Au, modulation the d band center of Pt, make OH easier desorption on Pt.
Fig. 5 for the sample for preparing according to embodiment 1 and comparative example 2 at 0.1M HClO 4Stability test (100mVs in solution -1, 0.6-1.0V vs.NHE) before and after CV curve and ORR polarization curve.As shown in Figure 5, after 10k circle CV scanning, the ECSAs of Pt/PdCo/C catalyst and ORR polarization curve half wave potential descend respectively 48.2% and 32mV; And through after the stability test of the same terms, the ECSAs of Pt/Au/PdCo/C catalyst is reduced to 104m from 144.3 2g -1, descend 27.9%, but the not significantly decay of ORR catalytic activity, half wave potential is the negative 13mV that moves only.The above results shows that the stability of Pt/Au/PdCo/C is significantly improved on the basis of Pt/PdCo/C.
Fig. 6 for the sample for preparing according to embodiment 1 and comparative example 2 at 0.1M HClO 4TEM photo in solution before and after stability test.As seen from Figure 6, before stability test, the nano particle in Pt/PdCo/C and Pt/Au/PdCo/C catalyst all is evenly distributed on the charcoal carrier, and average grain diameter is respectively 5.3 and 5.5nm.After 10k circle CV scanning, the serious gathering occurs in the nano particle in Pt/PdCo/C, and the surface becomes uneven, and the catalyst pattern has suffered heavy damage, causes the significantly decay of ECSAs and ORR catalytic activity in the CV curve.By contrast, through the Pt/Au/PdCo/C pattern of same electrochemical stability property testing, large change does not occur, just nano particle diameter slightly grow up (5.5 to 6.6nm).The above results shows, after introducing Au individual layer between Pt and PdCo, the stability of catalyst is significantly improved.

Claims (10)

1. Pt/Au/PdCo/C catalyst is characterized in that:
Catalyst is the metal core shell structure that carbon carries, and the metal in catalyst is take the PdCo alloy as core, and to be positioned at surperficial Pt as shell, Au is between Pt shell and PdCo core, and in catalyst, metal quality accounts for the 12-46% of gross mass; Wherein the mol ratio of Pd and Co is 5: 1-1: 1; The mol ratio of Pd and Au is 5: 1-12: 1; The mol ratio of Pd and Pt is 10: 1-20: 1.
2. the preparation method of the described catalyst of claim 1 is characterized in that: comprises the following steps,
(1) preparation of alloying PdCo/C
A. add PdCl in deionized water 2And/or Pd (NO 3) 2, add simultaneously Co (NO 3) 2, CoCl 2, CoBr 2, CoSO 4, Co (COOH) 2In one or more form mixtures, stir and make it to mix, add afterwards carbon carrier in mixed liquor, and ultrasonic to be dispersed to mixed liquor even;
B. drip sodium citrate aqueous solution in above-mentioned steps (1) a gained mixed liquor, and dropwise drip NaBH under the condition that stirs 4The aqueous solution filters to get solid matter after standing, adopts afterwards deionized water that the gained solid matter is washed, and after washing the gained material to be placed in vacuum drying oven dry, get PdCo/C;
C. step (1) b gained PdCo/C is heat-treated in hydrogen and inert gas gaseous mixture, get alloying PdCo/C;
(2) preparation of Pt/Au/PdCo/C catalyst
A. in ethanol, add above-mentioned steps (1) c gained alloying PdCo/C, stir and to add the Nafion emulsion after making it to mix, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (2) a gained mixed liquor, and be coated on the glass-carbon electrode surface as work electrode, the Pt silk is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (2) b gained work electrode is placed in H 2SO 4And CuSO 4Keep 1-300s in mixed solution under the sedimentation potential of 350-520mV, then electrode is immersed H 2SO 4And HAuCl 4In mixed solution and standing 1-10min carry out displacement reaction, then with deionized water, that electrode clean is clean;
D. above-mentioned steps (2) c gained work electrode is placed in H 2SO 4And CuSO 4Keep 1-300s in mixed solution under the sedimentation potential of 350-520mV, then electrode is immersed H 2SO 4And K 2PtCl 4In mixed solution and standing 1-10min carry out displacement reaction, then with deionized water, that electrode clean is clean, namely obtain the Pt/Au/PdCo/C catalyst.
3. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Pd in mixture described in step (1) a 2+And Co 2+Mol ratio be 5: 1-1: 1; Pd in described mixture 2+Concentration be 10-100mmol L -1
4. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Metal quality described in step (1) in alloying PdCo/C accounts for the 10-40% of gross mass.
5. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Described in step (1) b, the concentration of sodium citrate aqueous solution is 10-50mmol L -1, consumption is 10-50mL; Described NaBH 4The concentration of the aqueous solution is 10-100mmol L -1, consumption is 10-50mL; The described vacuumize time is 5-20 hour.
6. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Inert atmosphere described in step (1) c is one or two or more kinds the mixture in argon gas, helium, nitrogen; Described hydrogen volume accounts for the 1-10% of volume of gas; Described heat treatment temperature is 200-600 ℃; Described heat treatment time is 1-3h.
7. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Described in step (2) a, the concentration of PdCo/C in ethanol is 0.5-5mg mL -1The mass ratio of described Nafion and PdCo/C is 1: 10-1: 1.
8. the preparation method of catalyst as claimed in claim 2 is characterized in that:
H described in step (2) c and step (2) d 2SO 4And CuSO 4In mixed solution, both amount ratio is 5: 1-1: 2; Described H 2SO 4And HAuCl 4In mixed solution, both amount ratio is 100: 1-20: 1; Described H 2SO 4And K 2PtCl 4In mixed solution, both amount ratio is 100: 1-20: 1; H in above-mentioned three kinds of mixed solutions 2SO 4Concentration be 20-100mmol L -1
9. the preparation method of catalyst as claimed in claim 2 is characterized in that:
Described carbon carrier is: the mixture of one or more in XC-72R, BP2000, acetylene black, carbon nano-tube, graphite.
10. the application of the described Pt/Au/PdCo/C catalyst of claim 1 is characterized in that: described Pt/Au/PdCo/C catalyst can be used as metal air fuel cell oxygen reduction catalyst, Proton Exchange Membrane Fuel Cells oxygen reduction catalyst or direct liquid fuel battery oxygen reduction catalyst.
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CN104607206A (en) * 2015-02-05 2015-05-13 广西师范大学 Multiwalled carbon nanotube-loaded PtCo catalyst based on deep eutectic solvent, and preparation method and application of catalyst
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CN105032413A (en) * 2015-01-07 2015-11-11 宁波工程学院 Quick preparation method of Au-supported carbon nano-particles with visible light
CN105606674A (en) * 2015-12-22 2016-05-25 张利琴 Modified gold electrode and preparation method thereof
CN106669737A (en) * 2017-01-04 2017-05-17 上海应用技术大学 Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure
CN106925316A (en) * 2015-12-30 2017-07-07 北京大学 Gold/cementite C-base composte material and its preparation method and application
CN114792817A (en) * 2022-05-14 2022-07-26 北京亿华通科技股份有限公司 Co @ Pt core-shell type fuel cell catalyst with Au-doped subsurface layer and preparation method thereof

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CN104707603A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Pt-PbOx/C catalyst and preparation method thereof
CN105032413A (en) * 2015-01-07 2015-11-11 宁波工程学院 Quick preparation method of Au-supported carbon nano-particles with visible light
CN105032413B (en) * 2015-01-07 2017-06-30 宁波工程学院 The fast preparation method of the carbon nano-particle of visible ray load Au
CN104607206A (en) * 2015-02-05 2015-05-13 广西师范大学 Multiwalled carbon nanotube-loaded PtCo catalyst based on deep eutectic solvent, and preparation method and application of catalyst
CN105606674A (en) * 2015-12-22 2016-05-25 张利琴 Modified gold electrode and preparation method thereof
CN106925316A (en) * 2015-12-30 2017-07-07 北京大学 Gold/cementite C-base composte material and its preparation method and application
CN106925316B (en) * 2015-12-30 2019-07-23 北京大学 Gold/cementite C-base composte material and its preparation method and application
CN106669737A (en) * 2017-01-04 2017-05-17 上海应用技术大学 Preparation method of carbon/palladium/cobalt heterogeneous catalyst of magnetic core-shell structure
CN106669737B (en) * 2017-01-04 2019-05-24 上海应用技术大学 A kind of carbon/palladium-cobalt heterogeneous catalyst preparation method of magnetic core-shell structure
CN114792817A (en) * 2022-05-14 2022-07-26 北京亿华通科技股份有限公司 Co @ Pt core-shell type fuel cell catalyst with Au-doped subsurface layer and preparation method thereof

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