CN103638925A - Core-shell structure catalyst for fuel cells and its pulse electrodeposition preparation method - Google Patents
Core-shell structure catalyst for fuel cells and its pulse electrodeposition preparation method Download PDFInfo
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Abstract
The invention discloses a core-shell structure catalyst for fuel cells and its pulse electrodeposition preparation method. The active component of the catalyst is a nanoparticle with a core-shell structure, and an active metal is cladded in the form of an ultrathin shell on the surface of a carbon carrier loaded metal or alloy nanoparticle serving as a core. The catalyst takes a non-platinum noble metal or transition metal as the core, and adopts more than one of Pt, Ir or Au as the shell. The preparation method includes: preparation of the nanoparticle serving as the core, making of a working electrode for pulse electrodeposition, and preparation of the catalyst by pulse electrodeposition. The catalyst can be used as an anode or cathode catalyst of a low temperature fuel cell. The obtained catalyst has very high stability. Compared with underpotential deposition, the method is simple to operate, has no need for inert atmosphere protection, and is more suitable for large-scale industrial production, also can greatly reduce the noble metal consumption of fuel cells, and greatly reduce the cost of fuel cells, thus having great significance in promoting the commercialization process of fuel cells.
Description
Technical field
The present invention relates to fuel cell field, particularly relate to catalyst with core-casing structure material and preparation method thereof for a kind of fuel cell.
Background technology
A large amount of caused energy shortage problems of burning mineral fuel, and the greenhouse effects that cause due to a large amount of burning mineral fuels and serious atmosphere polluting problem increasingly severe, force people more and more to pay close attention to and explore new forms of energy and new energy conversion technology.In the thousands of solution having proposed at present, Proton Exchange Membrane Fuel Cells is considered to the most possible new technology that obtains in a short time a kind of environmental protection of application, and energy conversion efficiency is high owing to having for this technology, environmental friendliness, energy density advantages of higher have been subject to extensive concern.Past, fuel cell technology was all obtained larger breakthrough at material, equipment and technical elements during the last ten years, yet, use in a large number high cost that noble metal catalyst causes and the problems such as durability deficiency of fuel cell to hinder its development and commercialization process.
Nucleocapsid structure low-platinum catalyst is used relatively inexpensive and resourceful metal nanoparticle to make core, then at the platinum (or platinum alloy) of its surface coverage skim (or even monoatomic layer), thereby can realize the utilization rate that increases substantially noble metal platinum, reduce its use amount effective cost that reduces fuel cell, be therefore described as the place of the hope that is Proton Exchange Membrane Fuel Cells large-scale commercial.At present existing multiple technology of preparing and catalyst are suggested.
Mazumder etc. at 75 ℃, with oleamide and tert-butylamine borane reduction palladium acetylacetonate obtained particle diameter be the Pd nano particle of 5 nm as core, then synthesized the adjustable FePt shell of 1-3 nm thickness thereon.They have studied the relation between shell thickness and its hydrogen reduction activity, find that catalyst hydrogen reduction activity and stability when shell thickness is less than or equal to 1 nm are all better, shell thickness is that the Pd@FePt catalyst of the 1 nm current density when half wave potential is 0.7 V is 12 times of commercial catalysts, and demonstrates excellent stability in long-time CV test.(Mazumder V, Chi M, More K L, et al.
journal of the American Chemical Society, 2010, although 132:7848-7849.) this technology with two step chemical preparation catalyst with core-casing structure is widely studied, it uses a large amount of organic reagents mostly, environment is very unfriendly.And this method Artificial Control operation is very crucial, has so greatly limited its amount batch and produced.
Atomic layer deposition technology is widely used in the preparation of core-shell structure nanometer particle, and Weber etc. adopt and select region ALD technology at Al
2o
3on substrate, Pt is deposited on Pd core, obtains mean P t shell and be less than 0.8 nm, particle overall diameter is less than the Pd@Pt nucleocapsid structure particle of 5 nm, by adjusting size and the constituent of the adjustable particle of ALD program parameter.(Weber M J, Mackus A J M, Verheijen M A, et al.
chemistry of Materials, 2012,24:2973-2977.) still the cost of this method is higher, and is difficult to realize suitability for industrialized production, has limited the possibility of its practical application.
Zhou etc. obtain by underpotential deposition method the Pd that palladium cobalt alloy is core of take that Pt shell thickness only has 0.6 nm
2co@Pt cathod catalyst.The Pt mass activity ratio of this catalyst in CV is 0.72 A/mgPt(0.9V
vs.RHE), the current density of unit are catalyst is 0.5 mA/cm
2, compare with commercial catalysts, high 3.5 times and 2.5 times respectively.In addition, they have also studied the Pd that Pd3Fe (111) single crystal alloy is core
3fe@Pt catalyst.(Zhou?W?P，Sasaki?K，Su?D，et?al.?
The?Journal?of?Physical?Chemistry?C，2010，114：8950-8957)。It is a kind of new catalyst technology of preparing proposing in recent years that undercurrent potential method deposition technique is prepared catalyst with core-casing structure; the mass activity of the catalyst making can be greatly improved; yet; this technical program inert gas shielding, generation contained waste liquid, length consuming time, cost loaded down with trivial details, need to be strict is higher, is difficult to realize and produces in enormous quantities and practicality.
Chinese patent application 200810069271.7 discloses a kind of preparation method of core/shell structure perforated electrode catalyst, first this invention optionally deposits non-platinum family transition metal (Cu, Co, Ni) M " core " on the bonding gas perforated electrode of perfluorinated sulfonic resin, then this metal " core " and platinum salting liquid are carried out to displacement reaction and to obtain platinum layer, form M@Pt " core/shell " structure catalyst, the amplitude that the activity of the unit mass platinum of this catalyst increases is very limited.
Chinese patent application 200810070245.6 discloses a kind of method that indirect galvanic deposit is prepared carbon supported ultra-low platinum catalytic electrode.This invention changes deposit non-platinum family transition metal (Cu, Co, Ni) M " core " in the bonding gas perforated electrode previous step of perfluorinated sulfonic resin as four step depositional models into.Although this patent has been improved the problems such as the oversize and reunion of core metal grain to a certain extent, but the Electronic Speculum figure providing from it, they are still in 100 nanoscales, and this patent Electronic Speculum figure or out of Memory that catalyst that the method obtains is " core@shell " structure of failing to witness.
Chinese patent application 201210316227.8 discloses a kind of preparation method of efficient low platinum direct methanoic acid fuel cell catalyst, this patent adopts pulse electrodeposition method in titanium substrate, to deposit layer of Ni-P amorphous alloy as " core " of catalyst with core-casing structure, and then react on Ni-P amorphous alloy surface and form Pt layer by chemical replacement, as " shell " of catalyst with core-casing structure.This method has reduced the consumption of noble metal to a certain extent, improved the utilization rate of noble metal, but its particle is very large, from its Electronic Speculum figure, can find out and have 100 nm left and right, compared with macroparticle and be unfavorable for the catalytic performance of shell noble metal (Pt), can not realize the higher shell noble metal that utilizes, thereby make the mass activity of the standby catalyst with core-casing structure of this patent system there is no significant raising.And this patent is with aforesaid two patents Electronic Speculum figure or out of Memory that catalyst particle that the method obtains is " core shell " structure of equally failing to witness.
Generally speaking, in prior art, not yet find to use pulse electrodeposition method relatively inexpensive nanoparticle surface deposit active shell prepare particle diameter at 10 nm the patent report with the interior catalyst with core-casing structure applicable to fuel cell.
Summary of the invention
The invention discloses catalyst with core-casing structure and pulse electrodeposition preparation method thereof for a kind of fuel cell, this catalyst can be used for Proton Exchange Membrane Fuel Cells and other need to use the process of noble metal catalyst; The weak point of preparing catalyst with core-casing structure for current chemical deposition and current electro-deposition method, provides a kind of efficient, low-cost method of preparing high-performance catalyst with core-casing structure.
By methods such as high pressure organic sol methods, the nanometer particle load of the metal as core or alloy is being carried to core metal M/C through obtaining high dispersive carbon on pretreated carbon carrier; Then take shell metallic salting liquid as electro-deposition presoma, adopt constant current pulse electrodeposition method, adopt different Ton/Toff ratio (0.1-100), shell metallic is deposited on to M/C equably upper, obtain average grain diameter at the catalyst with core-casing structure of 5 nm left and right.
The active component of this catalyst is a kind of nano particle with nucleocapsid structure, active metal is usingd the form of ultra-thin shell and is coated on carbon carrier carried metal simple substance or the alloy nanoparticle sub-surface as core, the utilization rate of active metal is greatly enhanced, simultaneously, due to the interaction between shell atom and core, make the unit mass activity of active metal obtain the raising with respect to the several times of conventional nanocatalyst; Wherein, as the nano particle of core comprise non-platinum noble metals, transition metal, any two kinds of metals form in non-platinum noble metals and transition metal bianry alloy or in non-platinum noble metals and transition metal any three kinds of ternary alloy three-partalloys that metal forms, the size of the nano particle of core is at 1-10 nm; Active metal as shell comprises Pt, Ir, Au or two or three alloy forming in Pt, Ir, Au; Described carbon carrier comprises carbon black, CNT or Graphene; The quality group of described catalyst becomes: carbon carrier 50%-80%; Core metal or alloy 10%-40%, shell active metal or alloy 3%-15%; Described ultra-thin shell is comprised of 1-5 atomic layer; Described non-platinum noble metals comprises Ir, Rh, Ag, Au, Pd or Ru; Described transition metal comprises W, Mo, Ti, Cr, Co or Ni.
A pulse electrodeposition preparation method for catalyst with core-casing structure for fuel cell, its preparation method, comprises the following steps:
(1) prepare carbon carrier carried metal or the alloy nano particle as core: first carbon carrier is carried out to pretreatment, after using the nanometer particle load of the metal simple-substance as core or alloy on carbon carrier, obtain carbon carrier carried metal simple substance or alloy nano particle as core, i.e. substrate catalyst; Described metal simple-substance comprises Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described alloy comprises by Ru, Pd, Rh, Ir, Ag, Au, the bianry alloy of any two kinds of compositions or by Ru in Co or Ni, Pd, Rh, Ir, Ag, Au, the ternary alloy three-partalloy of any three kinds of compositions in Co or Ni; Described carbon carrier comprises XC-72R carbon black, CNT, Graphene; Metal simple-substance or the alloy nano particle load capacity on carbon carrier is 10wt%-40wt%, and the size of nano particle is 1-10 nm; Described using the nanometer particle load of the metal simple-substance as core or alloy, the method on carbon carrier is: dipping-reducing process, sodium borohydride reduction or high pressure organic sol method;
(2) for the making of the working electrode of pulse electrodeposition: be prepared from by method one or method two; Wherein method one is: take substrate catalyst, add in the alcohol solution that contains adhesive, catalyst pulp is made in ultrasonic dispersion, gets catalyst pulp and is coated in the surface as working electrode matrix, after being dried, makes the working electrode for pulse electrodeposition; Described adhesive comprises ptfe emulsion, perfluorinated sulfonic resin emulsion or fluorocarbon resin emulsion, and use amount mass percent is for accounting for the 1%-30% of catalytic amount in dry polymeric resin; Described alcohols comprises ethanol or isopropyl alcohol; Described working electrode matrix comprises vitreous carbon, platinized platinum, titanium sheet or platinized titanium sheet; Described dry mode comprises under infrared lamp irradiates dry in dry, baking oven or natural air drying is dry;
Method two is: substrate catalyst is directly added to the working solution that contains shell metallic for electro-deposition, and under stirring condition, the substrate catalyst of Contact cathod matrix forms working electrode;
(3) pulse electrodeposition, is placed in by the working electrode of making the 0.1 M HClO that nitrogen is saturated
4in solution, with the speed of sweeping of 50 mV/s, from open-circuit voltage, sweep to-0.3 ~-0.2 V, after 20 circles, under the current potential of-0.3 ~-0.2 V, suspend 2-4 min, realize the activation of substrate catalyst nanoparticle surface and reduction; After activation and reduction complete, rapidly electrode is proceeded in the electric depositing solution that contains shell metallic salt, complexing agent, conductive auxiliary agent that nitrogen is saturated, insert auxiliary electrode and reference electrode; Set pulse frequency, admittance and turn-off time, pulsed deposition total time, then start pulse electrodeposition, electro-deposition completes, and makes a kind of fuel cell catalyst with core-casing structure;
In above-mentioned preparation method, describedly carbon carrier is carried out to pretreatment be specially: take 5-20 g carbon carrier, add under 200-1000 mL acetone room temperature and stir 6-10 h, filter, washing, then vacuum drying at 60-70 ℃; By dried carbon dust 250-500 ℃ of roasting 2-3 h under nitrogen atmosphere protection, after add 200-800 mL 10% HNO
3with 100-400 mL 30% H
2o
2mixed liquor, adds hot reflux 6-10 h at 70-80 ℃, filters also and washs to neutrality with intermediate water, and vacuum drying 8-24 h in 60-80 ℃ of baking oven, grinds standbyly, obtains pretreated carbon carrier;
In above-mentioned preparation method, described high pressure organic sol method is specially: after natrium citricum is ground, add in the ethylene glycol solution of presoma, fully stirring, the ultrasonic natrium citricum that makes add pretreated carbon carrier 100--500mg after dissolving rapidly, between or ultrasonic and stirred for several all over after, more than adding KOH/ ethylene glycol solution adjusting pH to 10, proceed in the autoclave that is lined with tetrafluoroethene liner, put into baking oven 120-180 ℃ of reaction 8-10 h, reacted and be cooled to after room temperature, having added rare HNO
3adjust below pH to 5, then, with deionized water washing 3-5 time, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein in natrium citricum and presoma, the mol ratio of total metal is 1:1-5:1, and wherein presoma comprises that more than one in ruthenic chloride, palladium bichloride, gold chloride, iridium chloride, silver nitrate, cobalt nitrate, cobalt acetate, nickel acetate and radium chloride are below three kinds; The concentration range of described presoma in reaction system solution is 0.333-3.33mg/mL;
In above-mentioned preparation method, described sodium borohydride reduction is specially: weighing polyvinyl alcohol, adds 100-200 mL deionized water, in heating water bath, dissolve, then add precursor water solution, after stirring, with frozen water, prepare sodium borohydride aqueous solution, dropwise be added drop-wise in precursor water solution, stir, add carbon dust 100--500mg, stir 6-10 h, with deionized water washing, and be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein in polyvinyl alcohol and presoma, the mol ratio of metal is 5:1-20:1, and described presoma comprises chloroplatinic acid, gold chloride, palladium bichloride; The concentration range of described presoma in reaction system solution is 0.05-0.2 mg/mL;
In above-mentioned preparation method, described dipping-reducing process is specially: natrium citricum is added to precursor water solution, stir, add pretreated carbon dust 100--500mg, or ultrasonic and stirred for several all over after, at 60-80 ℃, oil bath solvent evaporated, then puts into vacuum drying oven 60-80 ℃ of dry 8-10 h, has been dried rear taking-up and has ground and put into tube furnace, under blanket of nitrogen, process 3-5h for 120-180 ℃.Then with deionized water washing 1-3 time, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein the mol ratio of natrium citricum and the total metal of presoma is 1:1-5:1; A kind of or two or more form of presoma in ruthenic chloride, palladium bichloride, iridium chloride wherein;
In above-mentioned preparation method, the active metal component that the described electric depositing solution of step (3) contains comprises: more than one in Pt, Au, Ir; Described shell metallic salt comprises more than one in dichloro four ammino platinum, chloroplatinic acid, gold chloride, iridous chloride; Complexing agent comprises citric acid or EDTA; Conductive auxiliary agent is sodium sulphate; The concentration of active metal component is 5-50 mM.
In above-mentioned preparation method, the mode of the pulse electrodeposition that step (3) adopts deposits making shell, and described pulse frequency is 100 – 10000 s
-1, each packet of pulses is containing an admittance time and a turn-off time, admittance time (t
on) be 0.00003 s to 0.001 s, turn-off time (t
off) be 0.00015 – 0.003 s, the ratio (t of admittance time and turn-off time
on/ t
off) beguine according to the difference of metal molar concentration in electrolyte difference, it is worth between 0.1-100; Total umber of pulse is 100-2000.
In above-mentioned preparation method, in step (3), the pulse current density of pulse electrodeposition is 1-10 mA/cm
2.
The catalyst of above-mentioned preparation method's gained, it has all shown good activity to the reduction of methanol oxidation, Oxidation of Formic Acid and oxygen, can be used as anode and the cathod catalyst of hydrogen-oxygen fuel cell, DMFC, direct methanoic acid fuel cell, the mass activity of the comparable common non-catalyst with core-casing structure of mass activity of its shell active metal component improves 2-10 doubly; In addition, this class catalyst also can be used as hydrogenation and the oxidation catalyst on chemical industry.
The present invention can also use the carbon-supported metal nano particle of business as the core of nucleocapsid catalyst.
Compared with prior art, fuel cell of the present invention has the following advantages with catalyst with core-casing structure material and preparation method thereof tool:
(1) fuel cell of the present invention can be as thin as 0.5-2.0 nm with the shell thickness of catalyst with core-casing structure, and the size of core-shell structure nanometer particle can be as small as 3-5 nm, can effectively improve the utilization rate of platinum, reduces its use amount.
(2) impulse electrodeposition technology proposed by the invention compared with prior art, easy and simple to handle except having, easily realize the advantage of large-scale industrial production, and before deposition, carried out after the scan round of original creation the pretreatment operation that short-term under negative potential is shelved reducing electrode surface, realize the activation of substrate catalyst nanoparticle surface and reduction; Be beneficial in subsequent step shell metallic in the deposition of substrate catalyst nanoparticle surface, thus the chemical property of the current efficiency while greatly having improved deposition and deposition rear catalyst.
(3) the prepared catalyst of the present invention all has extraordinary catalytic performance for the cathodic reduction of Methanol Anode oxidation reaction, formic acid anodic oxidation and oxygen, and the comparable commodity Pt/C of the activity catalyst of unit mass platinum improves 2-10 doubly;
(4) the prepared catalyst with core-casing structure of the present invention has good stability.
(5) carbon that the present invention makes carries catalyst with core-casing structure, have than business Pt/C catalyst exceed several times to the catalytic activity of methanol oxidation and for the catalytic activity of hydrogen reduction.
(6) in the present invention, high pressure organic sol method employing natrium citricum used is that complexing agent, ethylene glycol are solvent and reducing agent, in order to accelerate the rate of dissolution of natrium citricum in solvent ethylene glycol, adopted the way of grinding natrium citricum, accelerated greatly the rate of dissolution of natrium citricum in solvent, effectively shortened experiment consuming time, simplify experiment operation, reduced greatly energy consumption.
Accompanying drawing explanation
Fig. 1 is high-resolution-ration transmission electric-lens (HRTEM) figure of the prepared catalyst with core-casing structure Ru of embodiment 1@Pt/C.
Fig. 2 is high angle annular details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope (HAADF-STEM) figure of the prepared catalyst with core-casing structure Ru of embodiment 1@Pt/C.
Fig. 3 is the methanol oxidation apparent activity figure of catalyst in embodiment 1 and comparative example 1,2,3.
Fig. 4 be embodiment 1 with comparative example 1,2,3 in current density (in mA/ug.Pt) block diagram under the methanol oxidation spike potential of catalyst.
Fig. 5 is that the prepared catalyst with core-casing structure Ru of embodiment 1@Pt/C and comparative example's 3 commercial catalysts are to methanol oxidation stability test figure.
Fig. 6 is the hydrogen reduction apparent activity figure of catalyst in embodiment 1 and comparative example 1,2,3.
Fig. 7 is hydrogen reduction current density (in mA/ug.Pt) block diagram under 0.6 V (the Ag/AgCl electrode that reference is 3M) current potential of catalyst in embodiment 1 and comparative example 1,2,3.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated, and following examples are only used to more clearly set forth the present invention, but the scope of protection of present invention is not limited to the scope of following examples statement.
embodiment 1:Ru@Pt/C catalyst
(1) be used as the preparation of the Ru/C of core
(A) carbon dust XC-72 pretreatment:
Weigh in the balance and get 10 g VulcanXC-72 carbon dust (Cabot Corp., BET:237 m
2/ g, is abbreviated as C), add under 500 mL acetone room temperatures and stir 8 h to remove oxide and the organic impurities in carbon dust, filter and wash with intermediate water, then vacuum drying at 70 ℃; Dried carbon dust is transferred to tube furnace, and lower 500 ℃ of roasting 2 h of nitrogen atmosphere protection are to remove the impurity such as organic matter; Carbon dust is transferred in 500 mL there-necked flasks afterwards, added 200 mL 10% HNO
3with 100 mL 30% H
2o
2mixed liquor, adds hot reflux 6 h at 80 ℃, filters and washs to neutrality with intermediate water, and in 80 ℃ of baking ovens, vacuum drying 12 h, grind standby.
(B) high pressure organic sol method is prepared Ru/C
After the grinding of 385 mg, natrium citricum adds 9 mL ruthenium trichloride-ethylene glycol solutions (7.4 mg/mL), stir, add the pretreated carbon dust of 155.4 mg, between or ultrasonic and stirred for several all over after, more than adding KOH/ ethylene glycol solution adjusting pH to 10, proceed in the autoclave that is lined with tetrafluoroethene liner, put into 180 ℃ of reaction 8 h of baking oven, reacted and be cooled to after room temperature, having added rare HNO
3adjust below pH to 5.Then with deionized water washing 3-5 time, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber.
(2) adopt constant current impulse method to prepare Ru@Pt/C:
5 mg Ru/C add in the aqueous isopropanol of the perfluorinated sulfonic resin (Nafion) that 2 mL contain 0.15 wt%, and after ultrasonic one-tenth prepared Chinese ink shape slurry, get 5 uL slurries and be evenly coated on the glass-carbon electrode as working electrode matrix, and dry under infrared lamp;
Working electrode is placed in to the 0.1 M HClO that nitrogen is saturated
4in solution, with the speed of sweeping of 50 mV/s, from open-circuit voltage, sweep to-0.2 V, after 20 circles, under the current potential of-0.2 V, suspend 3min.
Then working electrode is proceeded to rapidly to the shell metallic salting liquid that nitrogen is saturated (dichloro four ammino platinum, concentration is 50 mM, sodium sulphate containing 0.1 M, the natrium citricum of 0.125 M), conduct is to electrode and reference electrode respectively to adopt platinum filament and Ag/AgCl electrode, and according to predefined constant current pulsed deposition program, (peak current density is 3 mA/cm
2, the admittance time is 0.3 ms, and the turn-off time is 0.15 ms, and umber of pulse is 1000, electrodeposition temperature is room temperature), obtaining Ru@Pt/C core-shell structure catalyst, theoretical platinum carrying capacity is 2.3 wt%.
The actual composition of catalyst can be determined by atomic absorption spectrum.Specific practice is: catalyst is washed out from electrode surface with ethanol, then add aqua regia dissolution, finally preparation becomes certain density solution, with atomic absorption spectrum, determines its concentration, finally converts and obtains the composition of catalyst.
(3) structural characterization of catalyst and performance test
(A) structural characterization of catalyst:
Use high-resolution-ration transmission electric-lens (HRTEM) to observe granularity and the distribution thereof of catalyst, use high angle annular details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope (HAADF-STEM) to observe the nucleocapsid structure of catalyst nanoparticles.
From Fig. 1 and Fig. 2, can find out, the average grain diameter of this catalyst is in 5 about nm (Fig. 1), and formed the Pt shell (Fig. 2) of one deck 1-2 nm left and right.From Fig. 2 (HAADF-STEM), can know and see that the lattice fringe of mid portion and the lattice fringe of periphery are inconsistent, illustrate that mid portion and periphery are respectively two kinds of different metals; From the shell metallic of can be the more figuratively bright employing impulse method deposition of two-part intensity, be that to be coated on core metal peripheral, rather than form alloy, neither form independent particle, peripherally compared with highlights, divide that to have 1-2nm can illustrate that shell is 1-2nm thick.
(B) methyl alcohol or the test of formic acid anodic oxidation catalytic performance:
Adopt three-electrode system, at 0.1 M HClO
4+ 1 M CH
3oH(or 0.1 M HClO
4+ 1 M HCOOH) in, with the speed of sweeping of 50 mV/s, carry out cyclic voltammetry scan, measured the catalytic activity of catalyst for Methanol Anode oxidation, the results are shown in Table 1 hurdle 1;
(C) oxygen cathode reduction catalysts performance test:
Adopt three-electrode system, at 0.1 saturated M HClO of oxygen
4in, with the speed of sweeping of 10 mV/s, the electrode rotating speed of 1600 r/min carries out cyclic voltammetry scan, the results are shown in Table 1 hurdle 1.
Except special instruction, catalyst involved in the present invention is all identical with above method of testing for the active method of testing of the cathodic reduction of the anodic oxidation of methyl alcohol/formic acid and oxygen.
comparative example 1: adopt constant current impulse method to prepare Pt/C(and be designated as Pt/C-P):
(1) preparation of carbon dust: operating procedure is identical with the step of (1) bar (A) in embodiment 1.
(2) Pt/C-P preparation: except adopting blank carbon dust to replace the Ru/C in embodiment 1, described in (2) bar of the other the same as in Example 1.
(3) catalyst test and sign: as described in Example 1, the catalytic activity of the cathodic reduction of Methanol Anode oxidation and oxygen is as shown in table 1 hurdle 13 for method.
comparative example 2: adopt direct current sedimentation to prepare Ru@Pt/C(and be designated as Ru@Pt/C-D):
(1) as the preparation of 30% Ru/C of core with embodiment 1.
(2) preparation of catalyst with core-casing structure Ru@Pt/C-D: except following explanation, the other the same as in Example 1.
Adopt direct current deposition to replace the pulsed deposition of embodiment 1, depositing current density is 3 mA/cm
2, sedimentation time is that the theoretical platinum deposition of 13 s. is 62 wt%.
(3) catalyst test and sign
Method, with embodiment 1, the results are shown in Table 1 hurdle 14
comparative example 3: the electrochemical property test of commercial catalysts JM4100:
Catalyst test method, with embodiment 1, the results are shown in Table 1 hurdle 15.
From Fig. 3, find out, in embodiment 1 and comparative example 1,2,3 in catalyst except the apparent activity of comparative example 1 catalyst that Direct precipitation obtains on carbon carrier is the poorest, the apparent activity of other several catalyst is more or less the same, the reason that causes this phenomenon is the upper activity of Pt that is not converted to unit mass, within the specific limits, better containing the many apparent activity of Pt amount.
Different catalysts mass ratio in comparison diagram 4 is active, can know and draw, the catalyst that adopts embodiment 1 pulsed deposition process to prepare has the highest activity on the Pt of unit mass (ug), thereby explanation pulsed deposition has obvious advantage.But directly on carbon carrier, pulsed deposition but obtains very poor performance, thus the effect that explanation core metal plays in catalyst, thus explanation catalyst with core-casing structure has obvious advantage.
As can be seen from Figure 5, the catalyst with core-casing structure that adopts embodiment 1 pulse electrodeposition to prepare has extraordinary stability, and after the circulation of 2000 circles, its performance has only reduced by 5%; And comparative example's 3 commercial catalysts front 20 circle in just have serious decay, during to 1000 circle its performance degradation 50%.
In conjunction with Fig. 6 and Fig. 7, can obtain the conclusion identical with methanol oxidation: it is active that the catalyst that 1, adopts pulsed deposition process to prepare has the highest hydrogen reduction on the Pt of unit mass (ug), thereby explanation pulsed deposition has obvious advantage.2, directly on carbon carrier, pulsed deposition but obtains very poor performance, thus the effect that explanation core metal plays in catalyst, thus explanation catalyst with core-casing structure has obvious advantage.
embodiment 2:Ru@Pt/C catalyst
(1) as the preparation of the 20%Ru/C of core: with embodiment 1.
(2) adopt constant current impulse method to prepare Ru@Pt/C:
Except following listed 2, the other the same as in Example 1
(A) shell metallic salting liquid (chloroplatinic acid, concentration 50 mM contain 0.1 M sodium sulphate, 0.125 M natrium citricum);
(B) pulse current density is 1 mA/cm
2, the pulse admittance time is 0.1 ms, and be 0.5 ms turn-off time, and umber of pulse is 1300.
(C) platinum content of catalyst is 2.5 wt%.
(3) catalyst performance test and sign, with embodiment 1, the results are shown in Table 1 hurdle 2.
embodiment 3:Ir@Pt/CNTs catalyst
Divided by CNT, replace XC-72R carbon black, with iridous chloride, replace outside ruthenium trichloride, other preparation and method of testing are completely identical with embodiment 1, the results are shown in Table 1 hurdle 3.
embodiment 4:Ru@Pt/rGO catalyst
Except following some difference, the other the same as in Example 1;
(1) catalyst carrier replaces XC-72 carbon black with reduced graphene;
(2) shell metallic salting liquid (chloroplatinic acid, concentration 5 mM contain 0.1 M sodium sulphate, 0.125 M EDTA);
(3) pulse current is 5 mA/cm
2, the admittance time is 0.1 ms, be 1.5 ms turn-off time;
(4) Pt theoretical deposition amount is 2%.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 4 with sign.
embodiment 5:RuAu@Pt/C catalyst
(1) as the preparation of the RuAu/C of core:
RuAu/C catalyst makes by sodium borohydride reduction.
First, take 22 mg polyvinyl alcohol, add 100 mL deionized waters, in 90 ℃ of heating water baths, dissolve.Then adding precursor water solution---2mL ruthenium trichloride solution (48.56mg/mL) and 85uL chlorauric acid solution (38.62mg/mL), after stirring, solution colour becomes dark reddish purple look from yellow.Then with frozen water, prepare sodium borohydride solution, be dropwise added drop-wise in above-mentioned solution, stir after 2 h make it to reduce completely, add 180 mg carbon dusts (preparation method with embodiment 1 is identical), stir 6 h, allow the abundant load of nano particle.Finally, with deionized water washing, and be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber.
(2) adopt constant current impulse method to prepare RuAu@Pt/C: with embodiment 4.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 5 with sign.
embodiment 6:IrCo@Pt/C catalyst
(1) as the preparation of the IrCo/C of core: the mixed solution with cobalt nitrate and iridous chloride has replaced ruthenium trichloride solution; Metal ion total concentration is constant; Other are with embodiment 1.
(2) adopt constant current impulse method to prepare IrCo@Pt/C: except following some difference, the other the same as in Example 1
(A) shell metallic salting liquid (dichloro four ammino platinum, concentration 5 mM contain 0.1 M sodium sulphate, 0.125 M natrium citricum);
(B) pulse current is 10 mA/cm
2, the admittance time is 0.3 ms, be 1.5 ms turn-off time
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 6 with sign.
embodiment 7:RhRu@Pt/C catalyst
(1) as the preparation of the RhRu/C of core: the mixed solution with radium chloride and ruthenic chloride has replaced ruthenium trichloride solution; Metal ion total concentration is constant, the other the same as in Example 1;
(2) adopt constant current impulse method to prepare RhRu@Pt/C: with embodiment 1
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 7 with sign.
embodiment 8:IrPd@AuPt/C catalyst
Except following some difference, the other the same as in Example 1;
(1) adopt infusion process preparation to add 4.75 mL palladium chloride solutions (5.9 mg/mL) and the 0.72mL iridous chloride aqueous solution (5.4 mg/mL) as the natrium citricum of the IrPd/C:269.92 mg of core, stir, add the pretreated carbon dust of 100 mg, between or ultrasonic and stirred for several all over after, at 70 ℃, oil bath solvent evaporated, then put into 70 ℃ of dry 10 h of vacuum drying oven, be dried rear taking-up and ground and put into tube furnace, under blanket of nitrogen, processed 3 h for 180 ℃.Then with deionized water washing 2 times, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber;
(2) adopt constant current impulse method to prepare IrPd@AuPt/C:
Shell metallic electro-deposition is implemented in two steps: first adopt constant current pulse method to prepare IrPd@Au/C, concrete enforcement (is just changed to chlorauric acid solution by electroplate liquid with the electro-deposition shell metallic Pt part of embodiment 1; Concentration 50 mM, containing 0.1 M sodium sulphate, 0.125 M natrium citricum), then continue to adopt constant current pulse method to prepare IrRu@AuPt/C the concrete electro-deposition shell metallic Pt part of implementing with embodiment 1.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 8 with sign.
embodiment 9:IrNi@AuPt/C catalyst
Except following some difference, the other the same as in Example 1;
(1) as the preparation of the IrNi/C of core: the mixed solution with iridous chloride and nickel acetate has replaced ruthenium trichloride solution, and metal ion total concentration is constant;
(2) adopt constant current impulse method to prepare IrNi@AuPt/C:
Shell metallic electro-deposition is implemented in two steps: first adopt constant current pulse method to prepare IrNi@Au/C, the concrete electro-deposition shell metallic Au part of implementing with embodiment 8; Then continue to adopt constant current pulse method to prepare IrNi@AuPt/C the concrete electro-deposition shell metallic Pt part of implementing with embodiment 1.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 9 with sign.
embodiment 10:Ru@Pt/C catalyst
Except following some difference, the other the same as in Example 1;
(1) support electrode for the preparation of working electrode is replaced to glassy carbon electrode with titanium electrode.
(2) adopt adhesive is replaced to perfluorinated sulfonic resin with ptfe emulsion, solvent is replaced isopropyl alcohol with ethanol, and the concentration of resin changes 0.25% into.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 10 with sign.
embodiment 11:Ru@Pt/C catalyst
Except following some difference, the other the same as in Example 1;
(1) support electrode for the preparation of working electrode is replaced to glassy carbon electrode with platinum electrode.
(2) adopt adhesive is replaced to perfluorinated sulfonic resin with fluorocarbon resin, solvent is replaced isopropyl alcohol with ethanol, and the concentration of resin changes 0.5% into.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 11 with sign.
embodiment 12:Ru@Pt/C catalyst
Except preparation method's difference of working electrode, the other the same as in Example 1;
Substrate catalyst is directly added to the working solution that contains shell metallic for electro-deposition, and under stirring state, the substrate catalyst that touches cathode base forms working electrode.
Catalyst test with embodiment 1, the results are shown in Table 1 hurdle 12 with sign.
From table 1, data can be found out, no matter active at methanol oxidation activity, the Oxidation of Formic Acid of anode the catalyst with nucleocapsid structure that adopts impulse method to prepare is, should in the hydrogen reduction activity of negative electrode, all the Pt/C catalyst than business 40% will, take Ru as core or Ir be core, when Pt is shell, the methanol oxidation Performance Ratio of catalyst performance is more excellent; And its hydrogen reduction performance is to take Ir as core, and when Pt is shell, performance is best; When take Pd and other metal alloys during as core, it is active that catalyst shows better Oxidation of Formic Acid.When take Ir, Pd alloy, be core, when Au, Pt are shell, no matter the catalyst of this special construction is the hydrogen reduction performance of anode methyl alcohol or Oxidation of Formic Acid or negative electrode if showing, and this kind of catalyst is one best in all catalyst.
The anode methyl alcohol of the obtained catalyst of each embodiment of table 1 or Oxidation of Formic Acid performance and cathodic oxygen reduction performance summary sheet
Claims (8)
1. a pulse electrodeposition preparation method for catalyst with core-casing structure for fuel cell, is characterized in that, comprises the following steps:
(1) prepare carbon carrier carried metal or the alloy nano particle as core: first carbon carrier is carried out to pretreatment, after using the nanometer particle load of the metal simple-substance as core or alloy on carbon carrier, obtain carbon carrier carried metal simple substance or alloy nano particle as core, i.e. substrate catalyst; Described metal simple-substance comprises Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described alloy comprises by Ru, Pd, Rh, Ir, Ag, Au, the bianry alloy of any two kinds of compositions or by Ru in Co or Ni, Pd, Rh, Ir, Ag, Au, the ternary alloy three-partalloy of any three kinds of compositions in Co or Ni; Described carbon carrier comprises XC-72R carbon black, CNT, Graphene; Metal simple-substance or the alloy nano particle load capacity on carbon carrier is 10wt%-40wt%, and the size of nano particle is 1-10 nm; Described using the nanometer particle load of the metal simple-substance as core or alloy, the method on carbon carrier is: dipping-reducing process, sodium borohydride reduction or high pressure organic sol method;
(2) for the making of the working electrode of pulse electrodeposition: be prepared from by method one or method two; Wherein method one is: take substrate catalyst, add in the alcohol solution that contains adhesive, catalyst pulp is made in ultrasonic dispersion, gets catalyst pulp and is coated in the surface as working electrode matrix, after being dried, makes the working electrode for pulse electrodeposition; Described adhesive comprises ptfe emulsion, perfluorinated sulfonic resin emulsion or fluorocarbon resin emulsion, and use amount mass percent is for accounting for the 1%-30% of catalytic amount in dry polymeric resin; Described alcohols comprises ethanol or isopropyl alcohol; Described working electrode matrix comprises vitreous carbon, platinized platinum, titanium sheet or platinized titanium sheet; Described dry mode comprises under infrared lamp irradiates dry in dry, baking oven or natural air drying is dry;
Method two is: substrate catalyst is directly added to the working solution that contains shell metallic for electro-deposition, and under stirring condition, the substrate catalyst of Contact cathod matrix forms working electrode;
(3) pulse electrodeposition, is placed in by the working electrode of making the 0.1 M HClO that nitrogen is saturated
4in solution, with the speed of sweeping of 50 mV/s, from open-circuit voltage, sweep to-0.3 ~-0.2 V, after 20 circles, under the current potential of-0.3 ~-0.2 V, suspend 2-4 min, realize the activation of substrate catalyst nanoparticle surface and reduction; After activation and reduction complete, rapidly electrode is proceeded in the electric depositing solution that contains shell metallic salt, complexing agent, conductive auxiliary agent that nitrogen is saturated, insert auxiliary electrode and reference electrode; Set pulse frequency, admittance and turn-off time, pulsed deposition total time, then start pulse electrodeposition, electro-deposition completes, and makes a kind of fuel cell catalyst with core-casing structure.
2. the pulse electrodeposition preparation method of catalyst with core-casing structure for fuel cell according to claim 1, it is characterized in that, describedly carbon carrier is carried out to pretreatment be specially: take 5-20 g carbon carrier, add under 200-1000 mL acetone room temperature and stir 6-10 h, filter, washing, then vacuum drying at 60-70 ℃; By dried carbon dust 250-500 ℃ of roasting 2-3 h under nitrogen atmosphere protection, after add 200-800 mL 10% HNO
3with 100-400 mL 30% H
2o
2mixed liquor, adds hot reflux 6-10 h at 70-80 ℃, filters also and washs to neutrality with intermediate water, and vacuum drying 8-24 h in 60-80 ℃ of baking oven, grinds standbyly, obtains pretreated carbon carrier;
Described high pressure organic sol method is specially: after natrium citricum is ground, add in the ethylene glycol solution of presoma, fully stirring, the ultrasonic natrium citricum that makes add pretreated carbon carrier 100--500mg after dissolving rapidly, between or ultrasonic and stirred for several all over after, more than adding KOH/ ethylene glycol solution adjusting pH to 10, proceed in the autoclave that is lined with tetrafluoroethene liner, put into baking oven 120-180 ℃ of reaction 8-10 h, reacted and be cooled to after room temperature, add rare HNO
3adjust below pH to 5, then, with deionized water washing 3-5 time, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein in natrium citricum and presoma, the mol ratio of total metal is 1:1-5:1, and wherein presoma comprises that more than one in ruthenic chloride, palladium bichloride, gold chloride, iridium chloride, silver nitrate, cobalt nitrate, cobalt acetate, nickel acetate and radium chloride are below three kinds; The concentration range of described presoma in reaction system solution is 0.333-3.33mg/mL;
Described sodium borohydride reduction is specially: weighing polyvinyl alcohol, add 100-200 mL deionized water, in heating water bath, dissolve, then add precursor water solution, after stirring, with frozen water, prepare sodium borohydride aqueous solution, be dropwise added drop-wise in precursor water solution, stir, add carbon dust 100--500mg, stir 6-10 h, with deionized water washing, and be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein in polyvinyl alcohol and presoma, the mol ratio of metal is 5:1-20:1, and described presoma comprises chloroplatinic acid, gold chloride, palladium bichloride; The concentration range of described presoma in reaction system solution is 0.05-0.2 mg/mL;
Described dipping-reducing process is specially: natrium citricum is added to precursor water solution, stir, add pretreated carbon dust 100--500mg, or ultrasonic and stirred for several all over after, at 60-80 ℃, oil bath solvent evaporated, then puts into vacuum drying oven 60-80 ℃ of dry 8-10 h, has been dried rear taking-up and has ground and put into tube furnace, under blanket of nitrogen, process 3-5h for 120-180 ℃, then, with deionized water washing 1-3 time, be placed in 70 ℃ of vacuum drying 12 h of vacuum drying chamber; Wherein the mol ratio of natrium citricum and the total metal of presoma is 1:1-5:1; A kind of or two or more form of presoma in ruthenic chloride, palladium bichloride, iridium chloride wherein.
3. the pulse electrodeposition preparation method of catalyst with core-casing structure for fuel cell according to claim 1, is characterized in that, the active metal component that the described electric depositing solution of step (3) contains comprises: more than one in Pt, Au, Ir; Described shell metallic salt comprises more than one in dichloro four ammino platinum, chloroplatinic acid, gold chloride, iridous chloride; Complexing agent comprises citric acid or EDTA; Conductive auxiliary agent is sodium sulphate; The concentration of active metal component is 5-50 mM.
4. the pulse electrodeposition preparation method of catalyst with core-casing structure for fuel cell according to claim 1, is characterized in that, the mode of the pulse electrodeposition that step (3) adopts deposits making shell, and described pulse frequency is 100 – 10000 s
-1, each packet of pulses is containing an admittance time and a turn-off time, admittance time (t
on) be 0.00003 s to 0.001 s, turn-off time (t
off) be 0.00015 – 0.003 s, the ratio (t of admittance time and turn-off time
on/ t
off) beguine according to the difference of metal molar concentration in electrolyte difference, it is worth between 0.1-100; Total umber of pulse is 100-2000.
5. the pulse electrodeposition preparation method of catalyst with core-casing structure for fuel cell according to claim 1, is characterized in that the pulse current density of pulse electrodeposition in step (3) is 1-10 mA/cm
2.
6. the fuel cell catalyst with core-casing structure being prepared by preparation method claimed in claim 1, it is characterized in that: the active component of this catalyst is a kind of nano particle with nucleocapsid structure, active metal is usingd the form of ultra-thin shell and is coated on carbon carrier carried metal simple substance or the alloy nanoparticle sub-surface as core; Wherein, as the nano particle of core comprise non-platinum noble metals, transition metal, any two kinds of metals form in non-platinum noble metals and transition metal bianry alloy or in non-platinum noble metals and transition metal any three kinds of ternary alloy three-partalloys that metal forms, the size of the nano particle of core is at 1-10 nm; Active metal as shell comprises Pt, Ir, Au or two or three alloy forming in Pt, Ir, Au; Described carbon carrier comprises carbon black, CNT or Graphene; The quality group of described catalyst becomes: carbon carrier 50%-80%; Core metal or alloy 10%-40%, shell active metal or alloy 3%-15%.
7. fuel cell catalyst with core-casing structure according to claim 6, is characterized in that: described ultra-thin shell is comprised of 1-5 atomic layer; Described non-platinum noble metals comprises Ir, Rh, Ag, Au, Pd or Ru; Described transition metal comprises W, Mo, Ti, Cr, Co or Ni.
8. fuel cell catalyst with core-casing structure according to claim 6, it is characterized in that: described catalyst has all shown good activity to the reduction of methanol oxidation, Oxidation of Formic Acid and oxygen, can be used as anode and the cathod catalyst of hydrogen-oxygen fuel cell, DMFC, direct methanoic acid fuel cell, the mass activity of the comparable common non-catalyst with core-casing structure of mass activity of its shell active metal component improves 2-10 doubly; In addition, this class catalyst also can be used as hydrogenation and the oxidation catalyst on chemical industry.
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