CN102881916A - 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 PDFInfo
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- CN102881916A CN102881916A CN2012103694087A CN201210369408A CN102881916A CN 102881916 A CN102881916 A CN 102881916A CN 2012103694087 A CN2012103694087 A CN 2012103694087A CN 201210369408 A CN201210369408 A CN 201210369408A CN 102881916 A CN102881916 A CN 102881916A
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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
Technical field
The present invention relates to a kind of gas-diffusion electrode that is loaded with the 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 that are loaded with the gas-diffusion electrode of two-layer core shell 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 oxygen reduction reaction remains Pt and alloy catalyst thereof.And limited reserves and the fancy price of Pt become one of business-like obstacle of fuel cell.How under the prerequisite that does not reduce catalyst activity, to improve its utilance and become recent study hotspot.
Adzic etc. find to form individual layer Cu atom by Cu-UPD on the noble metal surface, again 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 so that the ORR specific mass activity of such catalyst greatly improve.
Yet the preparation of present this nucleocapsid catalyst still is confined to the glass-carbon electrode surface, can't use in virtual electrode.Patent CN 100588018C is deposited on the nano particles such as transition metal Cu, Co or Ni on the porous carbon electrodes of perfluorinated sulfonic resin bonding by four step electrodeposition processes in the aqueous solution, then resulting electrode is immersed in the platinum salting liquid and makes the carbon platinum carried catalysis electrode by displacement reaction.Yet the electrode catalyst of this method preparation only limits to Cu, Co or Ni is the nano particle kernel, and because nucleocapsid structure occurs by displacement reaction, as controls improperly, and kernel obtains single component catalyst with complete reaction, 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 that is loaded with the two-layer core shell catalyst, one or more the mixture of catalyst in this gas-diffusion electrode in the catalyst layer in alloying PdCo/C or PdNi/C or PdFe/C or the PdCu/C is as the catalyst kernel, to be positioned at surperficial Pt as shell, take the Au between Pt shell and catalyst kernel as inner casing.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of gas-diffusion electrode that is loaded with the two-layer core shell catalyst, comprise the gas diffusion layers and the catalyst layer that are superimposed together, in gas diffusion layers surface in situ growth catalyst layer, catalyst in the catalyst layer is one or more among Pt/Au/PdCo/C or Pt/Au/PdNi/C or Pt/Au/PdFe/C or the Pt/Au/PdCu/C, catalyst is for take the PdCo/C of alloying or PdNi/C or PdFe/C or PdCu/C as nuclear, to be positioned at surperficial Pt as shell, the bivalve layer nucleocapsid catalyst take the Au between Pt shell and above-mentioned alloying nuclear as inner casing; Metal quality accounts for the 5-80% of gross mass in the catalyst layer; Wherein the mol ratio of the two or more summation among Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and the 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 comprised of supporting layer and microporous layers, supporting layer is carbon paper or the carbon cloth that PTFE emulsion hydrophobisation was processed, microporous layers for contain carbon dust and
The porous layer of resin, microporous layers are covered in supporting layer one side surface.
Described gas-diffusion electrode, the 12-46% that metal quality accounts for gross mass in the catalyst in the catalyst layer is excellent; Wherein the mol ratio of the two or more summation among Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and the Cu is that 5:1-1:1 is excellent; The mol ratio of Pd and Au is that 5:1-2:1 is excellent; The mol ratio of Pd and Pt is that 20:1-10:1 is excellent.
This gas-diffusion electrode has the advantages such as the noble metal carrying capacity is low, utilance is high, good stability during as metal air fuel cell negative electrode, fuel battery cathode with proton exchange film and direct liquid fuel battery negative electrode, but decrease fuel cell cost; The preparation method of this gas-diffusion electrode is simple simultaneously, is easy to batch production.
The preparation method of described its body diffusion electrode may further comprise the steps,
(1) preparation of gas diffusion layers: to adopt carbon paper that PTFE emulsion hydrophobisation processes or carbon cloth as supporting layer; With carbon dust, ethanol and
The slurries of emulsion mixed configuration evenly smear to supporting layer one side surface and prepare microporous layers;
(2) preparation of catalyst kernel:
A. in deionized water, add PdCl
2And/or Pd (NO
3)
2The mixture of one or more formation in the nitrate that one of adds simultaneously among Co, Ni, Fe, the Cu, chloride, bromide, sulfate, the acetate, stirring makes it to mix, and adds afterwards carbon carrier in mixed liquor, and ultrasonic to be dispersed to mixed liquor even;
B. in above-mentioned steps (1) a gained mixed liquor, drip sodium citrate aqueous solution, and under the condition that stirs, dropwise drip NaBH
4The aqueous solution filters to get solid matter after leaving standstill, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places vacuum drying oven dry after will washing, and gets a kind of among PdCo/C or PdNi/C or PdFe/C or the PdCu/C;
C. step (1) b gained PdCo/C or PdNi/C or PdFe/C or PdCu/C are heat-treated in hydrogen and inert gas gaseous mixture, get alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C;
D. repeat above-mentioned steps (2) a-c, prepare several times a kind of among above-mentioned alloying PdCo/C, PdNi/C, PdFe/C, the PdCu/C, or prepare several times two or more alloying PdCo/C, PdNi/C, PdFe/C and PdCu/C;
(3) preparation of nucleocapsid catalyst layer:
A. in ethanol, the mixture of one or more among adding above-mentioned steps (2) gained alloying PdCo/C or PdNi/C or PdFe/C or the PdCu/C stirs and makes it to mix rear adding
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface that is coated on step (1) gained gas diffusion layers is as work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed H
2SO
4And CuSO
4Under the sedimentation potential of 10-200mV, keep 10-300s in the mixed solution, make the alloying PdCo/C of working electrode surface or one or more the nanoparticle surface deposited monolayers Cu atom among PdNi/C or PdFe/C or the PdCu/C, then electrode is immersed H
2SO
4And HAuCl
4In the mixed solution and leave standstill 1-10min and make Au in the solution
3+With individual layer Cu atom generation displacement reaction, and guarantee that it reacts completely, the alloying nanoparticle surface that the Au atom is covered fully be coated in the gas diffusion layers surface, form the hypostracum of nucleocapsid catalyst, because the Cu atom of electro-deposition is single layer structure, so the Au atom that occurs after the displacement reaction still is single layer structure, with deionized water that electrode clean is clean more at last, being able to Au is shell, respectively take the PdCo/C of alloying or one or more the nucleocapsid catalyst layers as nuclear among PdNi/C or PdFe/C or the PdCu/C.
D. the work electrode that above-mentioned steps (3) c gained is loaded with nucleocapsid catalyst places H
2SO
4And CuSO
4Under the sedimentation potential of 10-200mV, keep 10-300s in the 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 the mixed solution and leave standstill 1-10min and make Pt in the solution
2+With individual layer Cu atom generation displacement reaction, and guarantee that it reacts completely, the nucleocapsid catalyst Au that the Pt atom is covered fully take Au as shell is surperficial, form the outer shell of nucleocapsid catalyst, because the Cu atom of electro-deposition is single layer structure, so the Pt atom that occurs after the displacement reaction still is single layer structure, with deionized water that electrode clean is clean more at last, namely obtain being loaded with take the PdCo/C of alloying or PdNi/C or PdFe/C or PdCu/C as nuclear, to be positioned at surperficial Pt as shell, the gas-diffusion electrode of one or more nucleocapsid catalysts among the bivalve layer Pt/Au/PdCo/C take the Au between Pt shell and above-mentioned alloying nuclear as inner casing or Pt/Au/PdNi/C or Pt/Au/PdFe/C or the Pt/Au/PdCu/C.
The preparation method of described gas-diffusion electrode, wherein Pd in the 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 the 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, wherein the metal quality in the alloying catalyst kernel described in the step (2) accounts for the 10-40% of gross mass.
The preparation method of described gas-diffusion electrode, wherein the concentration of sodium citrate aqueous solution is 10-50mmolL described in step (2) b
-1, add with respect to Pd
2+The 1-5 of equivalent molal quantity doubly; Described NaBH
4The concentration of the aqueous solution is 10-100mmolL
-1, add with respect 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 one or two or more kinds the mixture in argon gas, helium, the 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 the total concentration of alloying catalyst kernel in ethanol is 0.5-5mgmL described in step (3) a
-1Described
The mass ratio of dried resin and alloying catalyst 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
4The amount of the two is than being 5:1-1:2 in the mixed solution; Described H
2SO
4And HAuCl
4The amount of the two is than being 100:1-20:1 in the mixed solution; Described H
2SO
4And K
2PtCl
4The amount of the two is than being 100:1-20:1 in the mixed solution; H in above-mentioned three kinds of mixed solutions
2SO
4Concentration be 20-100mmolL
-1
Among 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, the graphite.
Described its body diffusion electrode 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 since the catalyst in its catalyst layer for take the PdCo/C of alloying or PdNi/C or PdFe/C or PdCu/C as nuclear, to be positioned at surperficial Pt as shell, bivalve layer nucleocapsid catalyst take the Au between Pt shell and above-mentioned alloying nuclear as inner casing, therefore its at first to have the 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, can realize the preparation of bivalve layer catalyst, and among the present invention with the inner casing of Au as nucleocapsid catalyst, effectively strengthened the stability of nucleocapsid catalyst; Again, when adopting the method for the invention to prepare gas-diffusion electrode, nuclear corrosion problem when the PdCo/C of employing alloying or PdNi/C or PdFe/C or PdCu/C have effectively avoided only adopting single metal (such as Fe, Co, Ni, Cu) for nuclear for nuclear can be prepared the gas-diffusion electrode of stable performance; At last, adopt the method for the invention to prepare gas-diffusion electrode,, adopt afterwards precious metal ion displacement Cu and be prepared in the method on nuclear or inner casing surface in alloying nuclear surface by underpotential deposition Cu, the thickness of shell can be effectively controlled, the noble metal carrying capacity can be effectively controlled; Simultaneously, gas-diffusion electrode of the present invention, its nucleocapsid catalyst adopts the method that directly makes in the gas diffusion layers surface and form catalyst layer to be prepared from, have reliability high, simple, be easy to change in batches the advantage such as product.
Description of drawings
Fig. 1 is that sweep speed is 20mVs at the stripping curve of different undercurrent potential deposit Cu (according to embodiment 1-5)
-1
Fig. 2 is under identical underpotential deposition condition, the stripping curve (according to embodiment 1,6-11) of the Cu of different underpotential deposition times of process, and sweep speed is 20mVs
-1
Fig. 3 is the sample for preparing according to embodiment 1, Comparative Examples 1 and 2 cyclic voltammetric (CV) curve in the saturated 0.1M HClO4 solution of nitrogen;
Fig. 4 for the sample for preparing according to embodiment 1, Comparative Examples 1 and 2 at the saturated 0.1M HClO of oxygen
4Oxygen reduction reaction in the solution (ORR) polarization curve, sweep speed is 10mVs
-1
Fig. 5 for the sample for preparing according to embodiment 1, Comparative Examples 1 at the saturated 0.1M HClO of oxygen
4Stability test curve in the solution.
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: be loaded with the preparation of the gas-diffusion electrode of Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst.
(1) preparation of gas diffusion layers:
At first, be 2 * 2cm with size
2After carbon paper (Toray TGP-060H) is weighed it is immersed into afterwards taking-up in 30 seconds in the 2wt.%PTFE emulsion fully, again weighs after then with hair-dryer it being dried up, and calculate the PTFE percentage composition that has leached thus.Repeat above-mentioned impregnation drying process, the PTFE carrying capacity to carbon paper is 10wt.%, and the carbon paper of afterwards hydrophobisation being processed places muffle furnace, and heat treatment 0.5h under 340 ° of C takes out after being down to room temperature, makes supporting layer.
Take by weighing 12mg
Then the XC-72 carbon dust adds ethanol 20ml, supersonic oscillations, and stir with glass bar, rear adding 5wt.% is uniformly dispersed
Solution (DuPont, EW=1100) 24mg makes in the slurries
The content of dried resin is 10wt.%, be stirred to mix after, the method that adopts blade coating in supporting layer one side surface, forms microporous layers with its blade coating, the carbon dust carrying capacity is 2mgcm in the microporous layers
-2
(2) preparation of catalyst kernel:
A. in the 100mL deionized water, add 26.6mg PdCl
2, add simultaneously 9.2mgCo (NO
3)
2(the Pd/Co atomic ratio is 3:1) stirred and to be made it to mix, and adds afterwards 80mg Vulcan XC-72 carbon dust and ultrasonic to be dispersed to mixed liquor even in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip 0.025M sodium citrate aqueous solution 25mL, then under rapid stirring, slowly drip 0.08M NaBH4 solution 50mL, filter to get solid matter after leaving standstill 30min, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places 80 ° of dry 8h of C vacuum drying oven after will washing, and obtains the PdCo/C catalyst;
C. with step (1) b gained PdCo/C in 400 ° of C, 5vol%H
2Heat treatment 2h can obtain the PdCo/C catalyst of alloying under the/Ar atmosphere;
(3) preparation of nucleocapsid catalyst layer:
A. in 4ml ethanol, add above-mentioned steps (2) gained alloying PdCo/C 10mg, stir and make it to mix rear adding 40mg 5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 0.8mg
PdCoCm
-2As work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed 50mM H
2SO
4And 50mMCuSO
4Mixed solution at 50mV(with respect to saturated calomel electrode) sedimentation potential under keep 120s, make Cu at PdCo/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mM H
2SO
4With 1mM HAuCl
4Mixed solution in and leave standstill 4min and make Au
3+With Cu displacement reaction occuring, get the Au/PdCo/C nucleocapsid catalyst, then adopts deionized water that electrode surface is cleaned up.
D. the work electrode that above-mentioned steps (3) c gained is loaded with the Au/PdCo/C nucleocapsid catalyst places 50mMH
2SO
4With 50mM CuSO
4In the mixed solution at 50mV(with respect to saturated calomel electrode) sedimentation potential under keep 120s, make Cu at Au/PdCo/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4And 1mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
The structure of confirming the Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst in the gas-diffusion electrode by Electronic Speculum for the PdCo alloy that carries take carbon as nuclear, 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 that is loaded with Pt/Au/PdCo/C bivalve layer nucleocapsid catalyst that makes under the different sedimentation potentials.
Difference from Example 1 is that the sedimentation potential among step (3) c and the d changes 30mV, 70mV, 100mV, 150mV into by 50mV respectively, and other steps are with embodiment 1.
In order to obtain the Cu individual layer of maximized surface coverage by UPD, sedimentation potential is optimized.Fig. 1 is at different sedimentation potential deposit 120s, then with 20mVs
-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.
Difference from Example 1 is that the sedimentation time among step (3) c and the d changes 10s, 30s, 60s, 180s and 240s into by 120s respectively, and other steps are with embodiment 1.
In order to obtain the Cu individual layer of maximized surface coverage by UPD, sedimentation time is optimized.Fig. 2 is with respect to saturated calomel electrode take 50mV() be sedimentation potential, through behind the different sedimentation times with 20mVs
-1Sweep speed scan the stripping curve that 650mV obtains the Cu individual layer from 50mV.By Fig. 2 finding, along with the prolongation of sedimentation time, the Anodic Stripping peak of Cu increases gradually, and curve overlaps behind the 120s, illustrate that the underpotential deposition of Cu is saturated, along with the further prolongation of sedimentation time no longer includes Cu at PdCo surface generation underpotential deposition.The phenomenon that this oneself stops in the UPD process comes from the strong interaction between Cu and the 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.
Embodiment 12: be loaded with the preparation of 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 the 10mL deionized water, add 23mg Pd (NO
3)
2, add simultaneously 14.9mgNi (COOH)
2(the Pd/Ni atomic ratio is 1:1) stirred and to be made it to mix, and adds afterwards 25mg BP2000 carbon dust and ultrasonic to be dispersed to mixed liquor even in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip 0.010M sodium citrate aqueous solution 50mL, then under rapid stirring, slowly drip 0.1M NaBH4 solution 50mL, filter to get solid matter after leaving standstill 30min, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places 80 ° of dry 5h of C vacuum drying oven after will washing, and obtains the PdNi/C catalyst;
C. with step (1) b gained PdNi/C in 200 ° of C, 10vol%H
2Heat treatment 3h can obtain the PdNi/C catalyst of alloying under the/Ar atmosphere;
(3) preparation of nucleocapsid catalyst layer:
A. in 4ml ethanol, add above-mentioned steps (2) gained alloying PdNi/C 10mg, stir and make it to mix rear adding 20mg 5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 0.6mg
PdNiCm
-2As work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed 100mM H
2SO
4And 100mMCuSO
4Mixed solution under the sedimentation potential of 50mV, keep 120s, make Cu at PdNi/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 100mM H
2SO
4With 1mM HAuCl
4Mixed solution in and leave standstill 4min and make Au
3+With Cu displacement reaction occuring, get the Au/PdNi/C nucleocapsid catalyst, then adopts deionized water that electrode surface is cleaned up.
D. the work electrode that above-mentioned steps (3) c gained is loaded with the Au/PdNi/C nucleocapsid catalyst places 100mMH
2SO
4With 100mM CuSO
4Under the sedimentation potential of 50mV, keep 120s in the mixed solution, make Cu at Au/PdNi/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 100mMH
2SO
4And 1mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/Au/PdNi/C bivalve layer nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
Embodiment 13: be loaded with the preparation of 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 the 10mL deionized water, add 115mg Pd (NO
3)
2, add simultaneously 16mgCuSO
4(the Pd/Cu atomic ratio is 5:1) stirred and to be made it to mix, and adds afterwards 540mg acetylene black carbon dust and ultrasonic to be dispersed to mixed liquor even in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip 0.050M sodium citrate aqueous solution 10mL, then under rapid stirring, slowly drip 0.1M NaBH4 solution 50mL, filter to get solid matter after leaving standstill 30min, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places 80 ° of dry 20h of C vacuum drying oven after will washing, and obtains the PdCu/C catalyst;
C. with step (1) b gained PdCu/C in 600 ° of C, 1vol%H
2Heat treatment 1h can obtain the PdCu/C catalyst of alloying under the/Ar atmosphere;
(3) preparation of nucleocapsid catalyst layer:
A. in 20ml ethanol, add above-mentioned steps (2) gained alloying PdCu/C 10mg, stir and make it to mix rear adding 200mg 5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 1.5mg
PdCuCm
-2As work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed 100mM H
2SO
4And 20mMCuSO
4Mixed solution under the sedimentation potential of 10mV, keep 300s, make Cu at PdCu/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 20mMH
2SO
4With 1mM HAuCl
4Mixed solution in and leave standstill 4min and make Au
3+With Cu displacement reaction occuring, get the Au/PdCu/C nucleocapsid catalyst, then adopts deionized water that electrode surface is cleaned up.
D. the work electrode that above-mentioned steps (3) c gained is loaded with the Au/PdCu/C nucleocapsid catalyst places 100mMH
2SO
4With 20mM CuSO
4Under the sedimentation potential of 10mV, keep 300s in the mixed solution, make Cu at Au/PdCu/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 20mMH
2SO
4And 1mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/Au/PdCu/C bivalve layer nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
Embodiment 14: be loaded with the preparation of 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 the 9mL deionized water, add 184mg Pd (NO
3)
2, add simultaneously 12.7mgFeCl
2(the Pd/Fe atomic ratio is 8:1) stirred and to be made it to mix, and adds afterwards 200mg Vulcan XC-72 carbon dust and ultrasonic to be dispersed to mixed liquor even in mixed liquor;
B. in above-mentioned steps (1) a gained mixed liquor, drip 0.040M sodium citrate aqueous solution 20mL, then under rapid stirring, slowly drip 0.1M NaBH4 solution 100mL, filter to get solid matter after leaving standstill 30min, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places 80 ° of dry 10h of C vacuum drying oven after will washing, and obtains the PdFe/C catalyst;
C. with step (1) b gained PdFe/C in 250 ° of C, 8vol%H
2Heat treatment 1.5h can obtain the PdFe/C catalyst of alloying under the/Ar atmosphere;
(3) preparation of nucleocapsid catalyst layer:
A. in 8ml ethanol, add above-mentioned steps (2) gained alloying PdFe/C 40mg, stir and make it to mix rear adding 160mg 5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 1.0mg
PdFeCm
-2As work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed 50mM H
2SO
4And 100mMCuSO
4Mixed solution under the sedimentation potential of 200mV, keep 10s, make Cu at PdFe/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4With 2.5mM HAuCl
4Mixed solution in and leave standstill 4min and make Au
3+With Cu displacement reaction occuring, get the Au/PdFe/C nucleocapsid catalyst, then adopts deionized water that electrode surface is cleaned up.
D. the work electrode that above-mentioned steps (3) c gained is loaded with the Au/PdFe/C nucleocapsid catalyst places 50mMH
2SO
4With 100mM CuSO
4Under the sedimentation potential of 200mV, keep 10s in the mixed solution, make Cu at Au/PdFe/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4And 2.5mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/Au/PdFe/C bivalve layer nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
Embodiment 15: be loaded with simultaneously the preparation of 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. adopt the preparation method of embodiment 1 to obtain alloying PdCo/C catalyst;
B. adopt the preparation method of embodiment 12 to obtain alloying PdNi/C catalyst;
C. adopt the preparation method of embodiment 13 to obtain alloying PdCu/C catalyst;
(3) preparation of nucleocapsid catalyst layer:
A. in 30ml ethanol, add step (2) gained alloying PdCo/C, PdNi/C and each 10mg of PdCu/C, stir and make it to mix rear adding 120mg5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 1.2mg
CatalystCm
-2As work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed 50mM H
2SO
4And 50mMCuSO
4Mixed solution under the sedimentation potential of 50mV, keep 120s, make Cu at alloying nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4With 1mM HAuCl
4Mixed solution in and leave standstill 4min and make Au
3+With Cu displacement reaction occuring, get Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nucleocapsid catalyst, then adopts deionized water that electrode surface is cleaned up.
D. the work electrode that above-mentioned steps (3) c gained is loaded with Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nucleocapsid catalyst places 50mMH
2SO
4And 50mMCuSO
4Under the sedimentation potential of 50mV, keep 120s in the mixed solution, make Cu at Au/PdCo/C, Au/PdNi/C and Au/PdCu/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4And 1mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/Au/PdCo/C, Pt/Au/PdNi/C and three kinds of bivalves of Pt/Au/PdCu/C layer nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
Comparative Examples 1: be loaded with the preparation of 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) be loaded with the preparation of the cathode catalyst layer of nucleocapsid catalyst:
A. with a of embodiment 1 step (3);
B. with the b of embodiment 1 step (3);
C. the work electrode that above-mentioned steps (3) b gained is loaded with the PdCo/C catalyst places 50mMH
2SO
4With 50mM CuSO
4Under the sedimentation potential of 50mV, keep 120s in the mixed solution, make Cu at PdCo/C nanoparticle surface generation underpotential deposition, then fast electrode is immersed 50mMH
2SO
4And 1mMK
2PtCl
4In the mixed solution and leave standstill 4min and make Pt in the solution
2+With Cu displacement reaction occuring, must be loaded with the gas-diffusion electrode of Pt/PdCo/C nucleocapsid catalyst, as the negative electrode of direct methanol fuel cell.
Comparative Examples 2: be loaded with the preparation of 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 a in embodiment 1 step (3) and two steps of b, without the c in embodiment 1 step (3) and d step;
Fig. 3 is PdCo/C(Comparative Examples 2), Pt/PdCo/C(Comparative Examples 1) and Pt/Au/PdCo/C(embodiment 1) the CV curve of catalyst.Compare with PdCo/C, obvious change has occured the CV curve of Pt/PdCo/C Catalytic Layer: 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 difficult reduction of platinum oxide.Identical with Pt/PdCo/C, the reduction peak current potential of oxide is also shuffled among the Pt/Au/PdCo/C, and the feature of convergence Pt shows that the Au on Au/PdCo surface is covered by Pt.
Fig. 4 is PdCo/C(Comparative Examples 2), Pt/PdCo/C(Comparative Examples 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.As seen, compare with PdCo/C, the hydrogen reduction electric current of Pt/PdCo/C obviously increases, and the electric current of Pd/Au/PdCo/C further increases.
Fig. 5 is Pt/PdCo/C(Comparative Examples 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 chronoamperometry that the stability of two kinds of catalyst is assessed, current potential is chosen 0.65V.As seen, obvious large than Pt/PdCo/C electrode of oxygen reduction reaction electric current on the Pt/Au/PdCo/C electrode, and electric current attenuation rate in time is lower than the latter, and namely stability is significantly improved.
Comparative Examples 3: be loaded with the preparation of 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, add again active carbon Vulcan XC-7280mg, stir and form uniform slurries.The NaBH4 aqueous solution 50mL that adds 0.1M in the above-mentioned slurries after continuing to stir half an hour, with black dope filtration, washing and dry, namely obtains the Co/C sample in vacuum drying oven.
B. get the resulting Co/C catalyst of a 10mg, add in the 4mL ethanol, stir and make it to mix rear adding 60 μ L 5%
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
C. pipette above-mentioned steps b gained mixed liquor, and microporous layers surface to the carrying capacity that is coated on step (1) gained gas diffusion layers is 0.8mg
CoCm
-2As cathode catalysis layer;
D. the diffusion layer that above-mentioned steps (2) c gained is loaded with the Co/C catalyst places 50mMH
2SO
4With 50mM CuSO
4Under the sedimentation potential of 50mV, keep 120s in the mixed solution, then fast electrode is immersed 50mM H
2SO
4With 1mM K
2PtCl
4In the mixed solution and leave standstill 4min, the Catalytic Layer that obtains is non-activity almost, and analyzing reason may be that base metal Co is corroded in sulfuric acid solution, can't be as the kernel of this method.
Claims (12)
1. be loaded with the gas-diffusion electrode of bivalve layer nucleocapsid catalyst, comprise the gas diffusion layers and the catalyst layer that are superimposed together, it is characterized in that:
Obtain the nucleocapsid catalyst layer in the gas diffusion layers surface in situ, catalyst in the catalyst layer is one or more among Pt/Au/PdCo/C or Pt/Au/PdNi/C or Pt/Au/PdFe/C or the Pt/Au/PdCu/C, catalyst is for take the PdCo/C of alloying or PdNi/C or PdFe/C or PdCu/C as nuclear, to be positioned at surperficial Pt as shell, bivalve layer nucleocapsid catalyst take the Au between Pt shell and above-mentioned alloying nuclear as inner casing, metal quality accounts for the 5-80% of gross mass in the catalyst layer; Wherein the mol ratio of the two or more summation among Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and the 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. gas-diffusion electrode as claimed in claim 1 is characterized in that:
Gas diffusion layers is comprised of supporting layer and microporous layers, and supporting layer is carbon paper or the carbon cloth that hydrophobisation was processed, microporous layers for contain carbon dust and
The porous layer of resin, microporous layers are covered in supporting layer one side surface.
3. gas-diffusion electrode as claimed in claim 1 is characterized in that:
In the catalyst layer in the catalyst metal quality account for the 12-46% of gross mass; Wherein the mol ratio of the two or more summation among Pd and Co or Ni or Fe or Cu or Co, Ni, Fe and the Cu is 5:1-1:1; The mol ratio of Pd and Au is 5:1-2:1; The mol ratio of Pd and Pt is 20:1-10:1.
4. the preparation method of described its body diffusion electrode of claim 1 is characterized in that: may further comprise the steps,
(1) preparation of gas diffusion layers: the carbon paper of processing take hydrophobisation or carbon cloth prepare microporous layers as supporting layer in supporting layer one side surface;
(2) preparation of catalyst kernel:
A. in deionized water, add PdCl
2And/or Pd (NO
3)
2The mixture of one or more formation in the nitrate that one of adds simultaneously among Co, Ni, Fe, the Cu, chloride, bromide, sulfate, the acetate, stirring makes it to mix, and adds afterwards carbon carrier in mixed liquor, and ultrasonic to be dispersed to mixed liquor even;
B. in above-mentioned steps (2) a gained mixed liquor, drip sodium citrate aqueous solution, and under the condition that stirs, dropwise drip NaBH
4The aqueous solution filters to get solid matter after leaving standstill, adopt afterwards deionized water that the gained solid matter is washed, and the gained material places vacuum drying oven dry after will washing, and gets a kind of among PdCo/C or PdNi/C or PdFe/C or the PdCu/C;
C. step (2) b gained PdCo/C or PdNi/C or PdFe/C or PdCu/C are heat-treated in hydrogen and inert gas gaseous mixture, get alloying PdCo/C or PdNi/C or PdFe/C or PdCu/C;
(3) preparation of nucleocapsid catalyst layer
A. in ethanol, the mixture of one or more among adding above-mentioned steps (2) gained alloying PdCo/C or PdNi/C or PdFe/C or the PdCu/C stirs and makes it to mix rear adding
Emulsion, and ultrasonic to be dispersed to mixed liquor even;
B. pipette above-mentioned steps (3) a gained mixed liquor, and the microporous layers surface that is coated on step (1) gained gas diffusion layers is as work electrode, the Pt sheet is to electrode, and saturated calomel electrode is reference electrode;
C. above-mentioned steps (3) b gained work electrode is placed H
2SO
4And CuSO
4Under the sedimentation potential of 10-200mV, keep 10-300s in the mixed solution, then electrode is immersed H
2SO
4And HAuCl
4In the mixed solution and leave standstill 1-10min and carry out displacement reaction, with deionized water that electrode clean is clean again;
D. above-mentioned steps (3) c gained work electrode is placed H
2SO
4And CuSO
4Under the sedimentation potential of 10-200mV, keep 10-300s in the mixed solution, then electrode is immersed H
2SO
4And K
2PtCl
4In the mixed solution and leave standstill 1-10min and carry out displacement reaction, with deionized water that electrode clean is clean again, namely obtain being loaded with take the PdCo/C of alloying or PdNi/C or PdFe/C or PdCu/C as nuclear, to be positioned at surperficial Pt as shell, the gas-diffusion electrode of one or more nucleocapsid catalysts among the bivalve layer Pt/Au/PdCo/C take the Au between Pt shell and above-mentioned alloying nuclear as inner casing or Pt/Au/PdNi/C or Pt/Au/PdFe/C or the Pt/Au/PdCu/C.
5. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
Pd in the 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 the 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
6. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
Metal quality described in the step (2) in the alloying catalyst kernel accounts for the 10-40% of gross mass.
7. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
The concentration of sodium citrate aqueous solution is 10-50mmolL described in step (2) b
-1, add with respect to Pd
2+The 1-5 of molar equivalent doubly; Described NaBH
4The concentration of the aqueous solution is 10-100mmolL
-1, add with respect to Pd
2+The 1-10 of molar equivalent doubly.
8. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
Inert atmosphere described in step (2) c is one or two or more kinds the mixture in argon gas, helium, the nitrogen; Described hydrogen volume accounts for the 1-10% of volume of gas; Described heat treatment temperature is 200-600 ° of C; Described heat treatment time is 1-3h.
9. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
The total concentration of alloying catalyst kernel in ethanol is 0.5-5mgmL described in step (3) a
-1Described
The mass ratio of dried resin and alloying catalyst kernel is 1:10-1:1.
10. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
H described in step (3) c and step (3) d
2SO
4And CuSO
4The amount of the two is than being 5:1-1:2 in the mixed solution; Described H
2SO
4And HAuCl
4The amount of the two is than being 100:1-20:1 in the mixed solution; Described H
2SO
4And K
2PtCl
4The amount of the two is than being 100:1-20:1 in the mixed solution; H in above-mentioned three kinds of mixed solutions
2SO
4Concentration be 20-100mmolL
-1
11. the preparation method of gas-diffusion electrode as claimed in claim 4 is characterized in that:
Described carbon carrier is: the mixture of one or more in XC-72, BP2000, acetylene black, carbon nano-tube, the graphite.
12. the application of the described gas-diffusion electrode of claim 1 is characterized in that:
Described its body diffusion electrode can be used as the negative electrode of metal air fuel cell, Proton Exchange Membrane Fuel Cells and direct liquid fuel battery.
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