CN102881916B - Gas diffusion electrode carried with double-shell core-shell catalyst and preparation and application thereof - Google Patents

Gas diffusion electrode carried with double-shell core-shell catalyst and preparation and application thereof Download PDF

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CN102881916B
CN102881916B CN201210369408.7A CN201210369408A CN102881916B CN 102881916 B CN102881916 B CN 102881916B CN 201210369408 A CN201210369408 A CN 201210369408A CN 102881916 B CN102881916 B CN 102881916B
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CN102881916A (en
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孙公权
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Amperex Technology Ltd Of Central China (zhangjiagang)
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Abstract

A gas diffusion electrode carried with a double-shell core-shell catalyst consists of a gas diffusion layer and a core-shell catalyst layer obtained on the gas diffusion layer in situ. A catalyst in the catalyst layer is the double-shell core-shell catalyst using a carbon-supported Pd alloy catalyst as a core, using Pt located on the surface as an outer shell and using Au located between the Pt shell and an alloying inner shell. A preparation method comprises three steps of (1) preparing the gas diffusion layer, (2) preparing the inner shell of the Pd alloy catalyst and (3) preparing the core-shell catalyst layer. When the gas diffusion electrode serves as a gas diffusion cathode for a metal air fuel cell, a proton exchange membrane fuel cell and a direct liquid fuel cell, the gas diffusion electrode has the advantages of being low in precious metal carrying capacity, high in utilization ratio, good in stability and the like, can remarkably reduce the fuel cell cost and is easily produced in a batch mode. In addition, the preparation method is simple and easy to operate.

Description

Be loaded with gas-diffusion electrode and the Synthesis and applications thereof of bivalve layer nucleocapsid catalyst
Technical field
The present invention relates to a kind of gas-diffusion electrode being loaded with two-layer core shell catalyst, relate in particular to a kind of gas-diffusion electrode for metal air fuel cell negative electrode, fuel battery cathode with proton exchange film and direct liquid fuel battery negative electrode.
The invention still further relates to the above-mentioned preparation method and application being loaded with the gas-diffusion electrode of two-layer core shell catalyst.
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 oxygen reduction reaction remains Pt and alloy catalyst thereof.And the limited reserves of Pt and fancy price one of obstacle becoming commercializing fuel cells.Under the prerequisite not reducing catalyst activity, how to improve the study hotspot that its utilance becomes recent.
Adzic etc. find 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 the preparation of current this nucleocapsid catalyst is still confined to glassy carbon electrode surface, cannot apply in virtual electrode.The nano particles such as transition metal Cu, Co or Ni are deposited on the porous carbon electrodes of perfluorinated sulfonic resin bonding by four step electrodeposition processes by patent CN 100588018C in aqueous, are then immersed in platinum salting liquid by obtained electrode and obtain carbon platinum carried catalysis electrode by displacement reaction.But electrode catalyst prepared by this method is only limitted to Cu, Co or Ni is nano particle kernel, and occurred by displacement reaction due to nucleocapsid structure, as improper in controlled, complete reaction is obtained single component catalyst by kernel, but not catalyst with core-casing structure.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to provide a kind of gas-diffusion electrode being loaded with two-layer core shell catalyst, catalyst in this gas-diffusion electrode in catalyst layer with the mixture of one or more in alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C for catalyst kernel, to be positioned at the Pt on surface for shell, with the Au between Pt shell and catalyst kernel for inner casing.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of gas-diffusion electrode being loaded with two-layer core shell catalyst, comprise the gas diffusion layers and catalyst layer that are superimposed together, in gas diffusion layers surface in situ growth catalyst layer, catalyst in catalyst layer is one or more in Pt/Au/PdCo/C or Pt/Au/PdNi/C or Pt/Au/PdFe/C or Pt/Au/PdCu/C, catalyst is for core with PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C, to be positioned at the Pt on surface for shell, the bivalve layer nucleocapsid catalyst being inner casing with the Au between Pt shell and above-mentioned alloying core; In catalyst layer, metal quality accounts for the 5-80% of gross mass; The mol ratio of the two or more summation wherein in Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and Cu is 8:1-1:2; The mol ratio of Pd and Au is 8:1-1:1; The mol ratio of Pd and Pt is 30:1-5:1.
Described gas-diffusion electrode, its gas diffusion layers is made up of supporting layer and microporous layers, and supporting layer is carbon paper or the carbon cloth of the process of PTFE emulsion hydrophobisation, microporous layers for containing carbon dust and the porous layer of resin, microporous layers is covered in supporting layer one side surface.
Described gas-diffusion electrode, the 12-46% that in catalyst layer, in catalyst, metal quality accounts for gross mass is excellent; The mol ratio of the two or more summation wherein in Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and Cu is 5:1-1:1 is excellent; The mol ratio of Pd and Au is 5:1-2:1 is excellent; The mol ratio of Pd and Pt is 20:1-10:1 is excellent.
When this gas-diffusion electrode is as metal air fuel cell negative electrode, fuel battery cathode with proton exchange film and direct liquid fuel battery negative electrode, there is the advantages such as noble metal carrying capacity is low, utilance is high, good stability, significantly can reduce fuel cell cost; The preparation method of this gas-diffusion electrode is simple simultaneously, is easy to batch production.
The preparation method of its body diffusion electrode described, comprises the following steps,
(1) preparation of gas diffusion layers: to adopt the carbon paper of PTFE emulsion hydrophobisation process or carbon cloth for supporting layer; With carbon dust, ethanol and the slurries uniform application of emulsion mixed configuration prepares microporous layers to supporting layer one side surface;
(2) preparation of catalyst kernel:
A. in deionized water, PdCl is added 2and/or Pd (NO 3) 2one or more mixtures formed in the nitrate one of simultaneously to add in Co, Ni, Fe, Cu, chloride, bromide, sulfate, acetate, stirring makes it to mix, and adds carbon carrier afterwards in mixed liquor, 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 the one in PdCo/C or PdNi/C or PdFe/C or PdCu/C;
C. step (1) b gained PdCo/C or PdNi/C or PdFe/C or PdCu/C is heat-treated in hydrogen and inert gas gaseous mixture, obtain alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C;
D. repeat above-mentioned steps (2) a-c, prepare the one in above-mentioned alloying PdCo/C, PdNi/C, PdFe/C, PdCu/C several times, or prepare two or more alloying PdCo/C, PdNi/C, PdFe/C and PdCu/C several times;
(3) preparation of nucleocapsid catalyst layer:
A. in ethanol, add one or more the mixture in above-mentioned steps (2) gained alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C, stir after making it to mix and add emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers being coated on step (1) gained gas diffusion layers is surperficial as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 10-200mV, maintain 10-300s in mixed solution, make one or more the nanoparticle surface deposited monolayers Cu atom in the alloying PdCo/C of working electrode surface or PdNi/C or PdFe/C or PdCu/C, then electrode is immersed H 2sO 4and HAuCl 4in mixed solution, also standing 1-10min makes the Au in solution 3+with individual layer Cu atom generation displacement reaction, and guarantee that it reacts completely, Au atom is covered completely be coated in the alloying nanoparticle surface on gas diffusion layers surface, form the hypostracum of nucleocapsid catalyst, Cu atom due to electro-deposition is single layer structure, therefore the Au atom occurred after displacement reaction is still single layer structure, last with deionized water, electrode clean is clean again, being able to Au is shell, respectively with the nucleocapsid catalyst layer that one or more in PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C are core.
D. work electrode above-mentioned steps (3) c gained being loaded with nucleocapsid catalyst is placed in H 2sO 4and CuSO 4under the sedimentation potential of 10-200mV, maintain 10-300s in mixed solution, make the nucleocapsid catalyst nanoparticle surface deposited monolayers Cu atom of working electrode surface, namely at Au atomic surface deposited monolayers Cu atom, then electrode is immersed H 2sO 4and K 2ptCl 4in mixed solution, also standing 1-10min makes the Pt in solution 2+with individual layer Cu atom generation displacement reaction, and guarantee that it reacts completely, Pt atom is covered completely with Au be the nucleocapsid catalyst Au surface of shell, form the outer shell of nucleocapsid catalyst, Cu atom due to electro-deposition is single layer structure, therefore the Pt atom occurred after displacement reaction is still single layer structure, last with deionized water, electrode clean is clean again, namely obtain being loaded with PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C as core, to be positioned at the Pt on surface for shell, the gas-diffusion electrode of one or more nucleocapsid catalysts in bivalve layer Pt/Au/PdCo/C or Pt/Au/PdNi/C or Pt/Au/PdFe/C or Pt/Au/PdCu/C being inner casing with the Au between Pt shell and above-mentioned alloying core.
The preparation method of described gas-diffusion electrode, wherein Pd in mixture described in step (2) a 2+and Co 2+, Ni 2+, Fe 2+, Cu 2+in the mol ratio of one or more summations be 5:1-1:1; Pd in described mixture 2+and Co 2+, Ni 2+, Fe 2+, Cu 2+in the concentration of one or more ion summations be 1-100mmolL -1.
The preparation method of described gas-diffusion electrode, the metal quality wherein in alloyed catalysts kernel described in step (2) accounts for the 10-40% of gross mass.
The preparation method of described gas-diffusion electrode, wherein described in step (2) b, the concentration of sodium citrate aqueous solution is 10-50mmolL -1, add relative to Pd 2+the 1-5 of equivalent mole number doubly; Described NaBH 4the concentration of the aqueous solution is 10-100mmolL -1, add relative to Pd 2+the 1-10 of molar equivalent doubly.
The preparation method of described gas-diffusion electrode, wherein inert atmosphere described in step (2) 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 ° of C.
The preparation method of described gas-diffusion electrode, wherein described in step (3) a, the total concentration of alloyed catalysts kernel in ethanol is 0.5-5mgmL -1; Described the mass ratio of dried resin and alloyed catalysts kernel is 1:10-1:1.
The preparation method of described gas-diffusion electrode, H described in described step (3) c and step (3) 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 20-100mmolL -1.
In the preparation method of described gas-diffusion electrode, described carbon carrier is one or more the mixture in XC-72, BP2000, acetylene black, carbon nano-tube, graphite.
Its body diffusion electrode described can be used as the negative electrode of metal air fuel cell, Proton Exchange Membrane Fuel Cells and direct liquid fuel battery.
Gas-diffusion electrode of the present invention due to the catalyst in its catalyst layer be for core with PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C, to be positioned at the Pt on surface for shell, the bivalve layer nucleocapsid catalyst being inner casing with the Au between Pt shell and above-mentioned alloying core, therefore its first to have precious metals pt utilance high, the advantages such as carrying capacity is low, effectively reduce the cost of fuel cell gas diffusion electrode; Secondly, adopt the method for the invention to prepare gas-diffusion electrode, the preparation of two lamella catalyst can be realized, and using the inner casing of Au as nucleocapsid catalyst in the present invention, effectively enhance the stability of nucleocapsid catalyst; Again, when adopting the method for the invention to prepare gas-diffusion electrode, adopt PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C to be that core effectively avoids and only adopts single metal (as Fe, Co, Ni, Cu) for nuclear corrosion problem during core, the gas-diffusion electrode of stable performance can be prepared; Finally, adopt the method for the invention to prepare gas-diffusion electrode, by underpotential deposition Cu in alloying core surface, adopt precious metal ion replace Cu and be prepared in the method for core or inner housing surface afterwards, effectively can control the thickness of shell, can effectively control noble metal carrying capacity; Meanwhile, gas-diffusion electrode of the present invention, its nucleocapsid catalyst adopts and directly to obtain in gas diffusion layers surface and the method forming catalyst layer is prepared from, have reliability high, simple, be easy to batch and change into the advantages such as product.
Accompanying drawing explanation
Fig. 1 is the stripping curve (according to embodiment 1-5) depositing Cu under different undercurrent potential, and sweep speed is 20mVs -1;
Fig. 2 is under identical underpotential deposition condition, and through the stripping curve (according to embodiment 1,6-11) of the Cu of different underpotential deposition time, sweep speed is 20mVs -1;
Cyclic voltammetric (CV) curve that Fig. 3 is the sample for preparing according to embodiment 1, comparative example 1 and 2 in the saturated 0.1M HClO4 solution of nitrogen;
Fig. 4 is the sample for preparing according to embodiment 1, comparative example 1 and 2 at the saturated 0.1M HClO of oxygen 4oxygen reduction reaction (ORR) polarization curve in solution, sweep speed is 10mVs -1;
Fig. 5 is the sample for preparing according to embodiment 1, comparative example 1 at the saturated 0.1M HClO of oxygen 4stability test curve in solution.
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: the preparation being loaded with the gas-diffusion electrode of Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers:
First, be 2 × 2cm by size 2it to be immersed in 2wt.%PTFE emulsion after weighing and to take out after 30 seconds by carbon paper (Toray TGP-060H) completely, again weighs, and calculate the PTFE percentage composition leached thus after then being dried up with hair-dryer.Repeat above-mentioned impregnation drying process, be 10wt.%, afterwards the carbon paper of hydrophobisation process be placed in muffle furnace to the PTFE carrying capacity in carbon paper, heat treatment 0.5h under 340 ° of C, takes out after being down to room temperature, obtained supporting layer.
Take 12mg xC-72 carbon dust, then adds ethanol 20ml, supersonic oscillations, and stirs with glass bar, adds 5wt.% after being uniformly dispersed solution (DuPont, EW=1100) 24mg, makes in slurries the content of dried resin is 10wt.%, is stirred to after mixing, and adopt the method for blade coating by its blade coating in supporting layer one side surface, form microporous layers, in microporous layers, carbon dust carrying capacity is 2mgcm -2.
(2) preparation of catalyst kernel:
A. in 100mL deionized water, 26.6mg PdCl is added 2, add 9.2mgCo (NO simultaneously 3) 2(Pd/Co atomic ratio is 3:1), stirs and makes it to mix, add 80mg Vulcan XC-72 carbon dust afterwards and ultrasonic disperse is even to mixed liquor in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, 0.025M sodium citrate aqueous solution 25mL is dripped, then 0.08M NaBH4 solution 50mL is slowly dripped under fast stirring, solid matter is filtered to obtain after leaving standstill 30min, deionized water is adopted to wash gained solid matter afterwards, and gained material after washing is placed in 80 ° of dry 8h of C vacuum drying oven, obtain PdCo/C catalyst;
C. by step (1) b gained PdCo/C in 400 ° of C, 5vol%H 2under/Ar atmosphere, heat treatment 2h can obtain the PdCo/C catalyst of alloying;
(3) preparation of nucleocapsid catalyst layer:
A. in 4ml ethanol, add above-mentioned steps (2) gained alloying PdCo/C 10mg, stir after making it to mix and add 40mg 5% emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 0.8mg to carrying capacity pdCocm -2as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in 50mM H 2sO 4and 50mMCuSO 4mixed solution at 50mV(relative to saturated calomel electrode) sedimentation potential under maintain 120s, make Cu at PdCo/C nanoparticle surface generation underpotential deposition, then quick electrode immersed 50mM H 2sO 4with 1mM HAuCl 4mixed solution in and leave standstill 4min make Au 3+there is displacement reaction with Cu, obtain Au/PdCo/C nucleocapsid catalyst, then adopt deionized water to be cleaned up by electrode surface.
D. work electrode above-mentioned steps (3) c gained being loaded with Au/PdCo/C nucleocapsid catalyst is placed in 50mMH 2sO 4with 50mM CuSO 4in mixed solution at 50mV(relative to saturated calomel electrode) sedimentation potential under maintain 120s, make Cu at Au/PdCo/C nanoparticle surface generation underpotential deposition, then quick electrode immersed 50mMH 2sO 4and 1mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst must be loaded with, as the negative electrode of direct methanol fuel cell.
The structure of the Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst confirmed in gas-diffusion electrode by Electronic Speculum be the PdCo alloy that carries with carbon for core, its surface is successively with metal A u and Pt metal.
Embodiment 2,3,4,5: in the same deposition time, the gas-diffusion electrode being loaded with Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst obtained under different sedimentation potential.
Difference from Example 1 is that the sedimentation potential in step (3) c and d changes 30mV, 70mV, 100mV, 150mV into by 50mV respectively, and other steps are with embodiment 1.
In order to be obtained the Cu individual layer of maximized surface coverage by UPD, sedimentation potential is optimized.Fig. 1 deposits 120s, then with 20mVs under different sedimentation potential -1sweep speed obtain the stripping curve of Cu individual layer from this electric potential scanning to 650mV.As seen from Figure 1, sedimentation potential is 50mV(vs.SCE) time, the stripping peak current of Cu has maximum.
Embodiment 6,7,8,9,10,11: in same potential, the gas-diffusion electrode being loaded with Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst obtained under different sedimentation time.
Difference from Example 1 is that the sedimentation time in step (3) c and d changes 10s, 30s, 60s, 180s and 240s into by 120s respectively, and other steps are with embodiment 1.
In order to be obtained the Cu individual layer of maximized surface coverage by UPD, sedimentation time is optimized.Fig. 2 is relative to saturated calomel electrode with 50mV() be sedimentation potential, with 20mVs after different sedimentation time -1sweep speed scan from 50mV the stripping curve that 650mV obtains Cu individual layer.By Fig. 2 finding, along with the prolongation of sedimentation time, the Anodic Stripping peak of Cu increases gradually, curve co-insides after 120s, illustrates that the underpotential deposition of Cu is saturated, and 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.
Embodiment 12: the preparation being loaded with the gas-diffusion electrode of Pt/Au/PdNi/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers: with embodiment 1;
(2) preparation of catalyst kernel:
A. in 10mL deionized water, 23mg Pd (NO is added 3) 2, add 14.9mgNi (COOH) simultaneously 2(Pd/Ni atomic ratio is 1:1), stirs and makes it to mix, add 25mg BP2000 carbon dust afterwards and ultrasonic disperse is even to mixed liquor in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, 0.010M sodium citrate aqueous solution 50mL is dripped, then 0.1M NaBH4 solution 50mL is slowly dripped under fast stirring, solid matter is filtered to obtain after leaving standstill 30min, deionized water is adopted to wash gained solid matter afterwards, and gained material after washing is placed in 80 ° of dry 5h of C vacuum drying oven, obtain PdNi/C catalyst;
C. by step (1) b gained PdNi/C in 200 ° of C, 10vol%H 2under/Ar atmosphere, heat treatment 3h can obtain the PdNi/C catalyst of alloying;
(3) preparation of nucleocapsid catalyst layer:
A. in 4ml ethanol, add above-mentioned steps (2) gained alloying PdNi/C 10mg, stir after making it to mix and add 20mg 5% emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 0.6mg to carrying capacity pdNicm -2as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in 100mM H 2sO 4and 100mMCuSO 4mixed solution under the sedimentation potential of 50mV, maintain 120s, make Cu at PdNi/C nanoparticle surface generation underpotential deposition, then quick electrode immersed 100mM H 2sO 4with 1mM HAuCl 4mixed solution in and leave standstill 4min make Au 3+there is displacement reaction with Cu, obtain Au/PdNi/C nucleocapsid catalyst, then adopt deionized water to be cleaned up by electrode surface.
D. work electrode above-mentioned steps (3) c gained being loaded with Au/PdNi/C nucleocapsid catalyst is placed in 100mMH 2sO 4with 100mM CuSO 4under the sedimentation potential of 50mV, maintain 120s in mixed solution, make Cu at Au/PdNi/C nanoparticle surface generation underpotential deposition, then quick electrode is immersed 100mMH 2sO 4and 1mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/Au/PdNi/C bivalve layer nucleocapsid catalyst must be loaded with, as the negative electrode of direct methanol fuel cell.
Embodiment 13: the preparation being loaded with the gas-diffusion electrode of Pt/Au/PdCu/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers: with embodiment 1;
(2) preparation of catalyst kernel:
A. in 10mL deionized water, 115mg Pd (NO is added 3) 2, add 16mgCuSO simultaneously 4(Pd/Cu atomic ratio is 5:1), stirs and makes it to mix, add 540mg acetylene black carbon dust afterwards and ultrasonic disperse is even to mixed liquor in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, 0.050M sodium citrate aqueous solution 10mL is dripped, then 0.1M NaBH4 solution 50mL is slowly dripped under fast stirring, solid matter is filtered to obtain after leaving standstill 30min, deionized water is adopted to wash gained solid matter afterwards, and gained material after washing is placed in 80 ° of dry 20h of C vacuum drying oven, obtain PdCu/C catalyst;
C. by step (1) b gained PdCu/C in 600 ° of C, 1vol%H 2under/Ar atmosphere, heat treatment 1h can obtain the PdCu/C catalyst of alloying;
(3) preparation of nucleocapsid catalyst layer:
A. in 20ml ethanol, add above-mentioned steps (2) gained alloying PdCu/C 10mg, stir after making it to mix and add 200mg 5% emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 1.5mg to carrying capacity pdCucm -2as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in 100mM H 2sO 4and 20mMCuSO 4mixed solution under the sedimentation potential of 10mV, maintain 300s, make Cu at PdCu/C nanoparticle surface generation underpotential deposition, then quick electrode immersed 20mMH 2sO 4with 1mM HAuCl 4mixed solution in and leave standstill 4min make Au 3+there is displacement reaction with Cu, obtain Au/PdCu/C nucleocapsid catalyst, then adopt deionized water to be cleaned up by electrode surface.
D. work electrode above-mentioned steps (3) c gained being loaded with Au/PdCu/C nucleocapsid catalyst is placed in 100mMH 2sO 4with 20mM CuSO 4under the sedimentation potential of 10mV, maintain 300s in mixed solution, make Cu at Au/PdCu/C nanoparticle surface generation underpotential deposition, then quick electrode is immersed 20mMH 2sO 4and 1mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/Au/PdCu/C bivalve layer nucleocapsid catalyst must be loaded with, as the negative electrode of direct methanol fuel cell.
Embodiment 14: the preparation being loaded with the gas-diffusion electrode of Pt/Au/PdFe/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers: with embodiment 1;
(2) preparation of catalyst kernel:
A. in 9mL deionized water, 184mg Pd (NO is added 3) 2, add 12.7mgFeCl simultaneously 2(Pd/Fe atomic ratio is 8:1), stirs and makes it to mix, add 200mg Vulcan XC-72 carbon dust afterwards and ultrasonic disperse is even to mixed liquor in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, 0.040M sodium citrate aqueous solution 20mL is dripped, then 0.1M NaBH4 solution 100mL is slowly dripped under fast stirring, solid matter is filtered to obtain after leaving standstill 30min, deionized water is adopted to wash gained solid matter afterwards, and gained material after washing is placed in 80 ° of dry 10h of C vacuum drying oven, obtain PdFe/C catalyst;
C. by step (1) b gained PdFe/C in 250 ° of C, 8vol%H 2under/Ar atmosphere, heat treatment 1.5h can obtain the PdFe/C catalyst of alloying;
(3) preparation of nucleocapsid catalyst layer:
A. in 8ml ethanol, add above-mentioned steps (2) gained alloying PdFe/C 40mg, stir after making it to mix and add 160mg 5% emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 1.0mg to carrying capacity pdFecm -2as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in 50mM H 2sO 4and 100mMCuSO 4mixed solution under the sedimentation potential of 200mV, maintain 10s, make Cu at PdFe/C nanoparticle surface generation underpotential deposition, then quick electrode immersed 50mMH 2sO 4with 2.5mM HAuCl 4mixed solution in and leave standstill 4min make Au 3+there is displacement reaction with Cu, obtain Au/PdFe/C nucleocapsid catalyst, then adopt deionized water to be cleaned up by electrode surface.
D. work electrode above-mentioned steps (3) c gained being loaded with Au/PdFe/C nucleocapsid catalyst is placed in 50mMH 2sO 4with 100mM CuSO 4under the sedimentation potential of 200mV, maintain 10s in mixed solution, make Cu at Au/PdFe/C nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mMH 2sO 4and 2.5mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/Au/PdFe/C bivalve layer nucleocapsid catalyst must be loaded with, as the negative electrode of direct methanol fuel cell.
Embodiment 15: the preparation being simultaneously loaded with the gas-diffusion electrode of Pt/Au/PdCo/C, Pt/Au/PdNi/C and Pt/Au/PdCu/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers: with embodiment 1.
(2) preparation of catalyst kernel:
A. the preparation method of embodiment 1 is adopted to obtain alloying PdCo/C catalyst;
B. the preparation method of embodiment 12 is adopted to obtain alloying PdNi/C catalyst;
C. the preparation method of embodiment 13 is adopted to obtain alloying PdCu/C catalyst;
(3) preparation of nucleocapsid catalyst layer:
A. in 30ml ethanol, add step (2) gained alloying PdCo/C, each 10mg of PdNi/C and PdCu/C, stir after making it to mix and add 120mg5% emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 1.2mg to carrying capacity catalystcm -2as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in 50mM H 2sO 4and 50mMCuSO 4mixed solution under the sedimentation potential of 50mV, maintain 120s, make Cu at alloying nanoparticle surface generation underpotential deposition, then quick electrode immersed 50mMH 2sO 4with 1mM HAuCl 4mixed solution in and leave standstill 4min make Au 3+there is displacement reaction with Cu, obtain Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nucleocapsid catalyst, then adopt deionized water to be cleaned up by electrode surface.
D. work electrode above-mentioned steps (3) c gained being loaded with Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nucleocapsid catalyst is placed in 50mMH 2sO 4and 50mMCuSO 4under the sedimentation potential of 50mV, maintain 120s in mixed solution, make Cu at Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mMH 2sO 4and 1mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/Au/PdCo/C, Pt/Au/PdNi/C and Pt/Au/PdCu/C tri-kinds of bivalve layer nucleocapsid catalysts must be loaded with, as the negative electrode of direct methanol fuel cell.
Comparative example 1: the preparation being loaded with the gas-diffusion electrode of Pt/PdCo/C nucleocapsid catalyst.
(1) preparation of gas diffusion layers: with embodiment 1 step (1);
(2) preparation of catalyst kernel: with embodiment 1 step (2);
(3) preparation of the cathode catalyst layer of nucleocapsid catalyst is loaded with:
A. with a of embodiment 1 step (3);
B. with the b of embodiment 1 step (3);
C. work electrode above-mentioned steps (3) b gained being loaded with PdCo/C catalyst is placed in 50mMH 2sO 4with 50mM CuSO 4under the sedimentation potential of 50mV, maintain 120s in mixed solution, make Cu at PdCo/C nanoparticle surface generation underpotential deposition, then quick electrode is immersed 50mMH 2sO 4and 1mMK 2ptCl 4in mixed solution, also standing 4min makes the Pt in solution 2+there is displacement reaction with Cu, the gas-diffusion electrode of Pt/PdCo/C nucleocapsid catalyst must be loaded with, as the negative electrode of direct methanol fuel cell.
Comparative example 2: the preparation being loaded with the gas-diffusion electrode of PdCo/C catalyst.
(1) preparation of gas diffusion layers: with embodiment 1 step (1);
(2) preparation of catalyst kernel: with embodiment 1 step (2);
(3) preparation of cathode catalyst layer: with two steps of a and b in embodiment 1 step (3), without the c in embodiment 1 step (3) and Step d;
Fig. 3 is PdCo/C(comparative example 2), Pt/PdCo/C(comparative example 1) and Pt/Au/PdCo/C(embodiment 1) the CV curve of catalyst.Compared with PdCo/C, the CV curve of Pt/PdCo/C Catalytic Layer there occurs obvious change: the Reduction of Oxide spike potential of 0.3-0.5V voltage belt is negative to be moved, and trends towards the reduction peak position of Pt, illustrates that the surface of PdCo is covered by Pt, and the more difficult reduction of platinum oxide.Identical with Pt/PdCo/C, in Pt/Au/PdCo/C, the reduction peak current potential of oxide is also shuffled, the feature of convergence Pt, show the Au on Au/PdCo surface cover by Pt.
Fig. 4 is PdCo/C(comparative example 2), Pt/PdCo/C(comparative example 1) and Pt/Au/PdCo/C(embodiment 1) polarization curves of oxygen reduction of catalyst in the saturated 0.1M high chloro acid solution of oxygen.Visible, compared with PdCo/C, the hydrogen reduction electric current of Pt/PdCo/C obviously increases, and the electric current of Pd/Au/PdCo/C increases further.
Fig. 5 is Pt/PdCo/C(comparative example 1) and Pt/Au/PdCo/C(embodiment 1) the hydrogen reduction stability test curve of catalyst in the saturated 0.1M high chloro acid solution of oxygen.Adopt the stability of chronoamperometry to two kinds of catalyst to assess, current potential chooses 0.65V.Visible, large obviously than Pt/PdCo/C electrode of oxygen reduction reaction electric current on Pt/Au/PdCo/C electrode, and electric current attenuation rate is in time lower than the latter, and namely stability is significantly improved.
Comparative example 3: the preparation being loaded with the gas-diffusion electrode of Pt/Co/C.
(1) preparation of gas diffusion layers: with embodiment 1 step (1);
(2) preparation of cathode catalyst layer:
A. in 10ml ethanol, add cobalt acetate 60mg, after stirring, then add active carbon Vulcan XC-7280mg, stir and form uniform slurries.In above-mentioned slurries, add the NaBH4 aqueous solution 50mL of 0.1M, after continuing to stir half an hour, black slurries are filtered, wash and dry in vacuum drying oven, namely obtain Co/C sample.
B. get the Co/C catalyst 10mg that a obtains, add in 4mL ethanol, stir after making it to mix and add 60 μ L 5% emulsion, and ultrasonic disperse is even to mixed liquor;
C. pipette above-mentioned steps b gained mixed liquor, and the microporous layers surface being coated on step (1) gained gas diffusion layers is 0.8mg to carrying capacity cocm -2as cathode catalysis layer;
D. diffusion layer above-mentioned steps (2) c gained being loaded with Co/C catalyst is placed in 50mMH 2sO 4with 50mM CuSO 4under the sedimentation potential of 50mV, maintain 120s in mixed solution, then quick electrode is immersed 50mM H 2sO 4with 1mM K 2ptCl 4also leave standstill 4min in mixed solution, the Catalytic Layer obtained almost non-activity, analyzing reason may be that base metal Co is corroded in sulfuric acid solution, cannot as the kernel of this method.

Claims (8)

1. be loaded with a preparation method for the gas-diffusion electrode of bivalve layer nucleocapsid catalyst, it is characterized in that: comprise the following steps,
(1) preparation of gas diffusion layers: with the carbon paper of hydrophobisation process or carbon cloth for supporting layer, prepare microporous layers in supporting layer one side surface;
(2) preparation of catalyst kernel:
A. in deionized water, PdCl is added 2and/or Pd (NO 3) 2one or more mixtures formed in the nitrate one of simultaneously to add in Co, Ni, Fe, Cu, chloride, bromide, sulfate, acetate, stirring makes it to mix, and adds carbon carrier afterwards in mixed liquor, and ultrasonic disperse is even to mixed liquor;
B. in above-mentioned steps (2) 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 the one in PdCo/C or PdNi/C or PdFe/C or PdCu/C;
C. step (2) b gained PdCo/C or PdNi/C or PdFe/C or PdCu/C is heat-treated in hydrogen and inert gas gaseous mixture, obtain alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C;
(3) preparation of nucleocapsid catalyst layer
A. in ethanol, add one or more the mixture in above-mentioned steps (2) gained alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C, stir after making it to mix and add emulsion, and ultrasonic disperse is even to mixed liquor;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers being coated on step (1) gained gas diffusion layers is surperficial as work electrode, Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 10-200mV, maintain 10-300s 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 (3) c gained work electrode is placed in H 2sO 4and CuSO 4under the sedimentation potential of 10-200mV, maintain 10-300s 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, with deionized water, electrode clean is clean again, namely obtain being loaded with PdCo/C or PdNi/C of alloying or PdFe/C or PdCu/C as core, to be positioned at the Pt on surface for shell, the gas-diffusion electrode of one or more nucleocapsid catalysts in bivalve layer Pt/Au/PdCo/C or Pt/Au/PdNi/C or Pt/Au/PdFe/C or Pt/Au/PdCu/C being inner casing with the Au between Pt shell and above-mentioned alloying core;
In catalyst layer, metal quality accounts for the 5-80% of gross mass; The mol ratio of the two or more summation wherein in Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and Cu is 8:1-1:2; The mol ratio of Pd and Au is 8:1-1:1; The mol ratio of Pd and Pt is 30:1-5:1.
2. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Pd in mixture described in step (2) a 2+and Co 2+, Ni 2+, Fe 2+, Cu 2+in the mol ratio of one or more summations be 5:1-1:1; Pd in described mixture 2+and Co 2+, Ni 2+, Fe 2+, Cu 2+in the concentration of one or more ion summations be 1-100mmolL -1.
3. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Metal quality in alloyed catalysts kernel described in step (2) accounts for the 10-40% of gross mass.
4. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Described in step (2) b, the concentration of sodium citrate aqueous solution is 10-50mmolL -1, the amount of substance of the natrium citricum added is Pd 2+the 1-5 of amount of substance doubly; Described NaBH 4the concentration of the aqueous solution is 10-100mmolL -1, the NaBH added 4amount of substance be Pd 2+the 1-10 of amount of substance doubly.
5. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Inert atmosphere described in step (2) 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.
6. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Described in step (3) a, the total concentration of alloyed catalysts kernel in ethanol is 0.5-5mgmL -1; Described the mass ratio of dried resin and alloyed catalysts kernel is 1:10-1:1.
7. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
H described in step (3) c and step (3) 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 20-100mmolL -1.
8. the preparation method of gas-diffusion electrode as claimed in claim 1, is characterized in that:
Described carbon carrier is: one or more the mixture in XC-72, BP2000, acetylene black, carbon nano-tube, graphite.
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