CN103165914B - 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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CN103165914B
CN103165914B CN201110421469.9A CN201110421469A CN103165914B CN 103165914 B CN103165914 B CN 103165914B CN 201110421469 A CN201110421469 A CN 201110421469A CN 103165914 B CN103165914 B CN 103165914B
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CN103165914A (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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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 Synthesis and applications thereof
Technical field
The present invention relates to a kind of oxygen reduction catalyst, relate to a kind of Synthesis and applications for metal air fuel cell oxygen reduction catalyst, Proton Exchange Membrane Fuel Cells oxygen reduction catalyst, direct liquid fuel battery oxygen reduction catalyst specifically.
Background technology
Along with the fuel such as coal, oil and natural gas consumption and day increases severely and the reserves of energy resources are day by day exhausted, the energy technology finding 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, has 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 one of reserves and the fancy price obstacle becoming commercializing fuel cells that Pt is limited.Under the prerequisite not reducing catalyst activity, how to improve the study hotspot that its utilance becomes recent.
Adzic seminar finds to form individual layer Cu atom by Cu-UPD at noble metal particle surfaces, then with Pt 2+carry out displacement and obtain Pt single-layer catalyst, wherein kernel generally adopts the noble metals such as Pd, Au and alloy thereof.The Pt of high degree of dispersion makes the ORR specific mass activity of such catalyst greatly improve.But, less in the research of electrochemical environment stability inferior for such catalyst.
Accelerated aging test is carried out to Pt/PdCo/C catalyst, with 100mV s in the potential range of 0.6-1.0V vs.NHE -1speed of sweeping carry out CV scanning, after 10k circle, the half wave potential of ORR polarization curve is negative moves 34mV, and catalytic activity obviously decays, and illustrates at the Pt individual layer electrochemical stability of catalyst surface high degree of dispersion poor.Au nano particle has good electrochemical stability, is introduced into the stability can improving eelctro-catalyst in eelctro-catalyst widely.But the ORR catalytic activity of Au itself is poor, if the active sites covering Pt when being introduced in catalyst may cause the reduction of catalytic activity.For this reason, Au is incorporated between surperficial Pt layer and PdCo core as secondary individual layer by the method that our design is replaced by Cu-UPD-, improves the electrochemical stability of Pt single-layer catalyst under being intended to not reduce 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 Synthesis and applications 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. in deionized water, PdCl is added 2and/or Pd (NO 3) 2, add Co (NO simultaneously 3) 2, CoCl 2, CoBr 2, CoSO 4, Co (COOH) 2in one or more, formed mixture, stir make it to mix, in mixed liquor, add carbon carrier afterwards, and ultrasonic disperse is even to mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip sodium citrate aqueous solution, and dropwise drip NaBH under rapid stirring 4the aqueous solution, filters to obtain solid matter after leaving standstill, and adopts deionized water to wash gained solid matter afterwards, and it is dry that gained material after washing is placed in vacuum drying oven, obtains PdCo/C;
C. step (1) b gained PdCo/C is heat-treated in hydrogen and inert gas gaseous mixture, obtain 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 after making it to mix and add Nafion emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (2) a gained mixed liquor, and be coated on glassy carbon electrode surface as work electrode, Pt silk and saturated calomel electrode are respectively to electrode and reference electrode;
C. above-mentioned steps (2) b gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 350-520mV, maintain 1-300s in mixed solution, then quick electrode is immersed H 2sO 4and HAuCl 4also leave standstill 1-10min in mixed solution and carry out displacement reaction, then with deionized water, electrode clean is clean;
D. above-mentioned steps (2) c gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 350-520mV, maintain 1-300s in mixed solution, then quick electrode is immersed H 2sO 4and K 2ptCl 4also leave standstill 1-10min in mixed solution and carry out displacement reaction, then with deionized water, electrode clean is clean, namely obtain 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 in alloying PdCo/C described in step (1) 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 DEG C, 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 -1; The 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, the thing mass ratio of the two is 5: 1-1: 2; Described H 2sO 4and HAuCl 4in mixed solution, the thing mass ratio of the two is 100: 1-20: 1; Described H 2sO 4and K 2ptCl 4in mixed solution, the thing mass ratio of the two is 100: 1-20: 1; Described H 2sO 4thing mass concentration be 20-100mmol L -1.
Described carbon carrier is: one or more the mixture 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, reduces the carrying capacity of Pt, thus reduces the cost of catalyst
2. the Au with good electrical chemical stability is incorporated between Pt shell and PdCo core, substantially increases ORR activity and the electrochemical stability of Pt single-layer catalyst.
Accompanying drawing explanation
Fig. 1 is the stripping curve (according to embodiment 1-5) of the Cu deposited under different undercurrent potential;
Fig. 2 is the stripping curve (according to embodiment 3 and 6-8) of the Cu through different time underpotential deposition;
Fig. 3 is that the sample for preparing according to embodiment 1 and comparative example 3 is at 0.1M HClO 4cyclic voltammetric (CV) curve in solution and oxygen reduction reaction (ORR) polarization curve;
Fig. 4 is that the sample for preparing according to embodiment 1 and comparative example 3 is at 0.1M HClO 4cV curve in solution before and after stability test and ORR polarization curve;
Fig. 5 is that the sample for preparing according to embodiment 1 and comparative example 3 is at 0.1M HClO 4tEM photo in solution before and after stability test;
Fig. 6 is that the sample for preparing according to embodiment 1 and comparative example 2 is 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.Certain the present invention is not limited in these specific embodiments.
Embodiment 1:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 120s in the sedimentation potential of 350mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmolL in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes Au 3+with Cu 2+there is displacement reaction, 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+there is displacement reaction, then with deionized water, electrode clean totally can be obtained Pt/Au/PdCo/C catalyst.
Embodiment 2:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 120s in the sedimentation potential of 370mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmolL in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes Au 3+with Cu 2+there is displacement reaction, 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+there is displacement reaction, then with deionized water, electrode clean totally can be obtained Pt/Au/PdCo/C catalyst.
Embodiment 3:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 120s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmolL in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes Au 3+with Cu 2+displacement reaction occurs, and then electrode surface cleans up by deionized water.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 electrode clean totally can be obtained Pt/Au/PdCo/C catalyst by deionized water.
Embodiment 4:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 120s in the sedimentation potential of 420mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmol L in solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes Au 3+with Cu 2+there is displacement reaction, 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+there is displacement reaction, then with deionized water, electrode clean totally can be obtained Pt/Au/PdCo/C catalyst.
Embodiment 5:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 120s in the sedimentation potential of 520mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmolL in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes Au 3+with Cu 2+there is displacement reaction, 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+there is displacement reaction, then with deionized water, electrode clean totally can be obtained Pt/Au/PdCo/C catalyst.
Embodiment 6:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 1s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmol L in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in solution, standing 4min makes Au 3+with Cu 2+displacement reaction occurs, and then electrode surface cleans up by deionized water.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 electrode clean totally can be obtained Pt/Au/PdCo/C catalyst by deionized water.
Embodiment 7:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu underpotential deposition is carried out: first maintain 40s in the sedimentation potential of 390mV and make Cu at PdCo nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mmol L in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in solution, standing 4min makes Au 3+with Cu 2+displacement reaction occurs, and then electrode surface cleans up by deionized water.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+there is displacement reaction, then with deionized water, electrode clean totally can be obtained Pt/Au/PdCo/C catalyst.
Embodiment 8:
Take 28.2mg PdCl 2with 9.6mg Co (NO 3) 2(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.By PdCo/C catalyst in 400 DEG C, 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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu-UPD is carried out: first maintain 300s in the sedimentation potential of 390mV and carry out CU-UPD, then quick electrode is immersed 50mmol L in mixed solution -1h 2sO 4with 1mmol L -1hAuCl 4in mixed solution, standing 4min makes displacement reaction carry out completely, then with deionized water, electrode clean is clean.Repeat Cu-UPD process, then electrode is placed in 50mmol L fast -1h 2sO 4and 1mmolL -1k 2ptCl 4in mixed solution, standing 4min makes displacement reaction carry out completely, then with deionized water, electrode clean totally can be obtained 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(Pd/Co atomic ratio is 3: 1) is dissolved in 100mL deionized water, adds 80mg Vulcan XC-72 carbon dust and ultrasonic disperse 30min.25mmol L is dripped after being uniformly dispersed -1sodium citrate aqueous solution 25mL, then slowly drips 80mmol L under fast stirring -1naBH 4solution 25mL.Filtered by the product obtained after 30min, a large amount of deionized water washing, 80 DEG C of dry 8h of vacuum drying oven, obtain PdCo/C catalyst.
PdCo/C catalyst is heat-treated (400 DEG C, 5vol%H 2/ Ar, 2h) the PdCo/C catalyst of alloying can be obtained.
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 and make binding agent.Pipette 20 μ L slurries after ultrasonic disperse 15min and be coated on glassy carbon electrode surface as work electrode.Work electrode is placed in 50mmol L -1h 2sO 4with 50mmol L -1cuSO 4cu-UPD is carried out: first maintain 120s in the sedimentation potential of 390mV and carry out Cu-UPD, then electrode is placed in 50mmol L fast in solution -1h 2sO 4with 1mmol L -1k 2ptCl 4in mixed solution, standing 4min makes displacement reaction carry out completely, then with deionized water, electrode clean totally can be obtained Pt/PdCo/C catalyst.
Comparative example 3:Pt/C catalyst
Commodity 20wt.%Pt/C catalyst (E-TEK company).
Fig. 1 deposits 120s, then with 20mV s under different sedimentation potential -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 being positioned at 470mV and 580mV increases gradually, starts to occur that body deposits the oxidation peak of Cu mutually when sedimentation potential is born and moved to 380mV, illustrate Cu under this current potential shedder deposit mutually, therefore sedimentation potential is chosen as 390mV.
Fig. 2 take 390mV as sedimentation potential, with 20mV s after different sedimentation time -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 after 120s, stripping curve overlaps substantially, illustrate that the underpotential deposition of Cu is saturated, the further prolongation along with sedimentation time no longer includes Cu, on PdCo surface, underpotential deposition occurs.The phenomenon that in UPD process, this oneself stops comes from the strong interaction between Cu and precious metals pd, and after Pd particle surface is wrapped up completely by Cu individual layer, Cu cannot stop at Cu atomic surface generation underpotential deposition.
Fig. 3 is that the sample for preparing according to embodiment 1 and comparative example 2 is at 0.1M HClO 4cV curve in solution and ORR polarization curve.As can be seen from Fig. 3 (a), compare with Pt/PdCo/C catalyst, the hydrogen adsorption desorption peak of Pt/Au/PdCo/C decreases, and the electrochemical active surface (ECSAs) calculated by integration hydrogen desorption peak is respectively 149.3 and 144.3m 2g -1, so high ECSAs may cause in catalyst surface high degree of dispersion due to Pt.In Pt/Au/PdCo/C catalyst, the redox peak of Pt when high potential all decreases and moves to high potential simultaneously, illustrates that OH is easier, on Pt surface, adsorption desorption occurs, imply that ORR catalytic activity will increase.From Fig. 3 (b), between Pt and PdCo, introduce the ORR catalytic activity that Au improves catalyst, the half wave potential of ORR polarization curve just moves to 0.90V by 0.878V, improves 22mV.
Fig. 4 be the dynamics current ratio of embodiment 1 and comparative example 2,3 (0.85V and 0.9V) unit mass Pt under certain potentials comparatively.As compared to Pt/C with Pt/PdCo/C catalyst, Pt/Au/PdCo/C catalyst ORR catalytic activity when 0.85V improves 13 and 4 times respectively, substantially increases the utilance of precious metals pt.The raising of ORR catalytic activity may be because adding of Au causes Pt Lattice Contraction, and the d of modulation Pt is with center, makes OH easier desorption on Pt.
Fig. 5 is that the sample for preparing according to embodiment 1 and comparative example 2 is 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, enclose after CV scanning through 10k, ECSAs and the ORR polarization curve half wave potential of Pt/PdCo/C catalyst declines 48.2% and 32mV respectively; And 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, decline 27.9%, but ORR catalytic activity does not significantly decay, half wave potential is only negative moves 13mV.The above results shows that the stability of Pt/Au/PdCo/C is significantly improved on the basis of Pt/PdCo/C.
Fig. 6 is that the sample for preparing according to embodiment 1 and comparative example 2 is 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 is all comparatively evenly distributed on high-area carbon, and average grain diameter is respectively 5.3 and 5.5nm.Enclose after CV scanning through 10k, the nano particle generation Severe aggregation in Pt/PdCo/C, and surface becomes uneven, catalyst pattern has suffered heavy damage, causes the significantly decay of ECSAs and ORR catalytic activity in CV curve.By contrast, there is not large change in the Pt/Au/PdCo/C pattern tested through same electrochemical stability, and just nano particle diameter slightly grows 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. a 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 with PdCo alloy for core, and to be positioned at the Pt on surface for shell, Au is between Pt shell and PdCo core, and in catalyst, Pt is single layer structure, and Au is time single layer structure; 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; Catalyst adopts the method for Cu-UPD-displacement to be incorporated between surperficial Pt layer and PdCo core as secondary individual layer by Au and prepares.
2. a preparation method for catalyst described in claim 1, is characterized in that: comprise the following steps,
(1) preparation of alloying PdCo/C
A. in deionized water, PdCl is added 2and/or Pd (NO 3) 2, add Co (NO simultaneously 3) 2, CoCl 2, CoBr 2, CoSO 4, Co (COOH) 2in one or more formed mixtures, stir make it to mix, in mixed liquor, add carbon carrier afterwards, and ultrasonic disperse is even to mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip sodium citrate aqueous solution, and dropwise drip NaBH under the condition stirred 4the aqueous solution, filters to obtain solid matter after leaving standstill, and adopts deionized water to wash gained solid matter afterwards, and it is dry that gained material after washing is placed in vacuum drying oven, obtains PdCo/C;
C. step (1) b gained PdCo/C is heat-treated in hydrogen and inert gas gaseous mixture, obtain 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 after making it to mix and add Nafion emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (2) a gained mixed liquor, and be coated on glassy carbon electrode surface as work electrode, 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 4under the sedimentation potential of 350-520mV, maintain 1-300s in mixed solution, then electrode is immersed H 2sO 4and HAuCl 4also leave standstill 1-10min in mixed solution and carry out displacement reaction, then with deionized water, electrode clean is clean;
D. above-mentioned steps (2) c gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 350-520mV, maintain 1-300s in mixed solution, then electrode is immersed H 2sO 4and K 2ptCl 4also leave standstill 1-10min in mixed solution and carry out displacement reaction, then with deionized water, electrode clean is clean, namely obtain 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 in alloying PdCo/C described in step (1) 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 the mixture of one or two or more kinds in argon gas, helium, nitrogen; Described hydrogen volume accounts for the 1-10% of volume of gas; Described heat treatment temperature is 200-600 DEG C; 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 -1; The 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, the thing mass ratio of the two is 5:1-1:2; Described H 2sO 4and HAuCl 4in mixed solution, the thing mass ratio of the two is 100:1-20:1; Described H 2sO 4and K 2ptCl 4in mixed solution, the thing mass ratio of the two 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: one or more the mixture in XC-72R, BP2000, acetylene black, carbon nano-tube, graphite.
10. an application for Pt/Au/PdCo/C catalyst described in 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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