CN103638925B - A kind of fuel cell catalyst with core-casing structure and pulse electrodeposition preparation method thereof - Google Patents
A kind of fuel cell catalyst with core-casing structure and pulse electrodeposition preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fuel cell catalyst with core-casing structure and pulse electrodeposition preparation method thereof, the active component of this catalyst is the nano particle with nucleocapsid structure, and active metal is coated on carbon carrier carried metal as core or alloy nanoparticle sub-surface using the form of ultra-thin shell; This catalyst using non-platinum noble metals or transition metal as core, using Pt, Ir or Au more than one as shell.Preparation method is: as the preparation of the nano particle of core, the making of the working electrode of pulse electrodeposition, and pulse electrodeposition prepares catalyst; This catalyst can be used as anode or the cathod catalyst of low-temperature fuel cell; The catalyst of gained has very high stability, and compare with underpotential deposition, it is easy and simple to handle, without the need to inert atmosphere protection, is more suitable for large-scale industrial production.And significantly can reduce the noble metal use amount of fuel cell, significantly reduce the cost of fuel cell, to promoting that the commercialization process of fuel cell is significant.
Description
Technical field
The present invention relates to fuel cell field, particularly relate to a kind of fuel cell catalyst with core-casing structure material and preparation method thereof.
Background technology
Energy shortage problem caused by a large amount of burning mineral fuel, and the greenhouse effects to cause due to a large amount of burning mineral fuel 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 proposed at present, Proton Exchange Membrane Fuel Cells is considered to the new technology most possibly obtaining a kind of environmental protection of application in a short time, and energy conversion efficiency is high owing to having for this technology, environmental friendliness, energy density advantages of higher receive extensive concern.Past, fuel cell technology all achieved larger breakthrough in material, equipment and technique during the last ten years, but the problems such as the durability deficiency of the high cost that a large amount of use noble metal catalyst causes and fuel cell hinder its development and commercialization process.
Nucleocapsid structure low-platinum catalyst uses cheaper and resourceful metal nanoparticle to make core, then at the platinum (or platinum alloy) of its surface coverage skim (or even monoatomic layer), thus can realize increasing substantially noble metal platinum utilization, reduce its use amount and effective cost reducing fuel cell, be therefore described as the place of the hope being Proton Exchange Membrane Fuel Cells large-scale commercial.Existing multiple technology of preparing and catalyst are suggested at present.
Mazumder etc. at 75 DEG C, with oleamide and tert-butylamine borane reduction palladium acetylacetonate obtain particle diameter be the Pd nano particle of 5 nm as core, then synthesized the FePt shell that 1-3 nm thickness is adjustable thereon.They have studied the relation between shell thickness and its oxygen reduction activity, find catalytic oxygen reduction activity when shell thickness is less than or equal to 1 nm and stability all better, 12 times of shell thickness to be the current density of Pd@FePt catalyst when half wave potential is 0.7 V of 1 nm be commercial catalysts, and excellent stability is demonstrated in long-time CV test.(Mazumder V, Chi M, More K L, et al.
journal of the American Chemical Society, 2010,132:7848-7849.) although this technology with two step chemical preparation catalyst with core-casing structure is widely studied, it uses a large amount of organic reagents mostly, and environment is very unfriendly.And this method Artificial Control operation is very crucial, greatly limit its amount batch like this and produce.
Atomic layer deposition technology is widely used in the preparation of core-shell structure nanometer particle, and Weber etc. adopt selected zone ALD technology at Al
2o
3pt is deposited on Pd core by substrate, 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 size and the constituent of the adjustable particle of adjustment ALD program parameter.(Weber M J, Mackus A J M, Verheijen M A, et al.
chemistry of Materials, 2012,24:2973-2977.) but the cost of this method is higher, and be difficult to realize suitability for industrialized production, limit the possibility of its practical application.
That Zhou etc. obtain that Pt shell thickness only has 0.6 nm by underpotential deposition method take Pd-Co alloy as the Pd of core
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, compared with commercial catalysts, high 3.5 times and 2.5 times respectively.In addition, they are investigated Pd3Fe (111) single crystal alloy is the Pd of 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 proposed in recent years that undercurrent potential method deposition technique prepares catalyst with core-casing structure; the mass activity of obtained catalyst can be greatly improved; but; this technical program is loaded down with trivial details, need strict inert gas shielding, produce contained waste liquid, consuming time longer, cost is higher, be difficult to realize to produce in enormous quantities and practical.
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 group transition metal (Cu, Co, Ni) M " core " on the gas perforated electrode that perfluorinated sulfonic resin is bonding, then this metal " core " and platinum salting liquid are carried out displacement reaction and form M@Pt " core/shell " structure catalyst to obtain platinum layer, 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 prepares carbon supported ultra-low platinum catalytic electrode.This invention changes gas perforated electrode previous step deposition non-platinum group transition metal (Cu, Co, Ni) M " core " bonding at perfluorinated sulfonic resin into four step depositional models.Although this patent improves the problems such as the excessive and reunion of core metal grain size to a certain extent, but from the Electronic Speculum figure that it provides, they are still in 100 nanoscales, and the catalyst that the method obtains and this patent fails to witness is Electronic Speculum figure or the out of Memory of " core@shell " structure.
Chinese patent application 201210316227.8 discloses a kind of preparation method of efficient low platinum direct methanoic acid fuel cell catalyst, this patent adopts electrodeposition method in titanium substrate, deposit " core " of layer of Ni-P amorphous alloy as catalyst with core-casing structure, and then form Pt layer, as " shell " of catalyst with core-casing structure by chemical replacement reaction on Ni-P amorphous alloy surface.This method reduces the consumption of noble metal to a certain extent, improve the utilization rate of noble metal, but its particle is very large, can find out there are about 100 nm from its Electronic Speculum figure, comparatively macroparticle be unfavorable for the catalytic performance of shell noble metal (Pt), can not realize higher utilizing shell noble metal, thus 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 Electronic Speculum figure or the out of Memory of " core shell " structure with aforesaid two patents equally fail to witness catalyst particle that the method obtains.
Generally speaking, in prior art, not yet find to use electrodeposition method to prepare the patent report that be applicable to the catalyst with core-casing structure of fuel cell of particle diameter within 10 nm at the nanoparticle surface position activity shell of cheaper.
Summary of the invention
The invention discloses a kind of fuel cell catalyst with core-casing structure and pulse electrodeposition preparation method thereof, this catalyst can be used for Proton Exchange Membrane Fuel Cells and other needs to use the process of noble metal catalyst; Prepare the weak point of catalyst with core-casing structure for current chemical deposition and current electro-deposition method, a kind of efficient, method that low cost prepares high-performance catalyst with core-casing structure is provided.
By methods such as high pressure organic sol methods, the nanometer particle load as the metal of core or alloy is carried core metal M/C obtaining high dispersive carbon on pretreated carbon carrier; Then with shell metallic salting liquid for electro-deposition presoma, adopt constant current electrodeposition method, adopt different Ton/Toff ratio (0.1-100), shell metallic is deposited on M/C equably, obtain the catalyst with core-casing structure of average grain diameter at about 5 nm.
The active component of this catalyst is a kind of nano particle with nucleocapsid structure, active metal is coated on carbon carrier carried metal simple substance as core or alloy nanoparticle sub-surface using the form of ultra-thin shell, the utilization rate of active metal is greatly enhanced, simultaneously, due to the interaction between shell atom and core, the unit mass of active metal activity is made to obtain the raising of the several times relative to conventional nano catalyst; Wherein, the ternary alloy three-partalloy that nano particle as core comprises non-platinum noble metals, transition metal, the bianry alloy be made up of two kinds of metals any in non-platinum noble metals and transition metal or is made up of three kinds of metals any in non-platinum noble metals and transition metal, the size of the nano particle of core is at 1-10 nm; Active metal as shell comprises Pt, Ir, Au or by two or three alloy formed 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 made up 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 fuel cell catalyst with core-casing structure, its preparation method, comprises the following steps:
(1) the carbon carrier carried metal as core or alloy nano particle is prepared: first carbon carrier is carried out pretreatment, after using as the metal simple-substance of core or alloy nanometer particle load on the carbon carrier, obtain the carbon carrier carried metal simple substance as core or alloy nano particle, i.e. substrate catalyst; Described metal simple-substance comprises Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described alloy comprises by the bianry alloy of two kinds of compositions any in Ru, Pd, Rh, Ir, Ag, Au, Co or Ni or the ternary alloy three-partalloy by three kinds of compositions any in Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described carbon carrier comprises XC-72R carbon black, CNT, Graphene; Metal simple-substance or alloy nano particle load capacity is on the carbon carrier 10wt%-40wt%, and the size of nano particle is 1-10 nm; Describedly using as the metal simple-substance of core or the nanometer particle load method on the carbon carrier of alloy be: impregnation-reduction method, 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, and add in the alcohol solution containing adhesive, ultrasonic disperse makes catalyst pulp, gets catalyst pulp and is coated in surface as working electrode matrix, namely obtain the working electrode for pulse electrodeposition after drying; Described adhesive comprises ptfe emulsion, perfluorinated sulfonic resin emulsion or fluorocarbon resin emulsion, and use amount mass percent is the 1%-30% accounting for 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 platinum plating titanium sheet; The mode of described drying is irradiated dry in dry, baking oven under comprising infrared lamp or natural air drying is dry;
Method two is: substrate catalyst is directly added for electro-deposition containing in the working solution of shell metallic, under stirring condition, the substrate catalyst of Contact cathod matrix forms working electrode;
(3) pulse electrodeposition, is placed in the 0.1 M HClO that nitrogen is saturated by the working electrode made
4in solution, sweep to-0.3 ~-0.2 V with the speed of sweeping of 50 mV/s from open-circuit voltage, under the current potential of-0.3 ~-0.2 V, suspend 2-4 min after 20 circles, realize the activation to substrate catalyst nanoparticle surface and reduction; After activation and reduction complete, rapidly electrode is proceeded in the saturated electric depositing solution containing shell metallic salt, complexing agent, conductive auxiliary agent of nitrogen, insert auxiliary electrode and reference electrode; Setting pulse frequency, admittance and turn-off time, pulsed deposition total time, then start pulse electrodeposition, electro-deposition completes, i.e. obtained a kind of fuel cell catalyst with core-casing structure;
In above-mentioned preparation method, describedly carbon carrier is carried out pretreatment be specially: take 5-20 g carbon carrier, add 200-1000 mL acetone stirred at ambient temperature 6-10 h, filter, washing, then vacuum drying at 60-70 DEG C; By dried carbon dust 250-500 DEG C 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 DEG C, and filter and wash to neutrality with intermediate water, in 60-80 DEG C of baking oven, vacuum drying 8-24 h, grinds for subsequent use, obtains pretreated carbon carrier;
In above-mentioned preparation method, described high pressure organic sol method is specially: add in the ethylene glycol solution of presoma after being ground by natrium citricum, abundant stirring, ultrasonic natrium citricum is dissolved rapidly after add pretreated carbon carrier 100--500mg, between or ultrasonic and stirred for several all over after, add KOH/ ethylene glycol solution and regulate more than pH to 10, proceed in the autoclave being lined with tetrafluoroethene liner, put into baking oven 120-180 DEG C of reaction 8-10 h, react and after being cooled to room temperature, added rare HNO
3adjust below pH to 5, then spend deionized water 3-5 time, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; Wherein in natrium citricum and presoma, the mol ratio of total metal is 1:1-5:1, and wherein presoma comprises more than one less than three kinds in ruthenic chloride, palladium bichloride, gold chloride, iridium chloride, silver nitrate, cobalt nitrate, cobalt acetate, nickel acetate and radium chloride; 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, dissolve in heating water bath, then add precursor water solution, after stirring, prepare sodium borohydride aqueous solution with frozen water, dropwise be added drop-wise in precursor water solution, stir, add carbon dust 100--500mg, stir 6-10 h, spend deionized water, and be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; 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 impregnation-reduction method is specially: natrium citricum is added precursor water solution, stir, add pretreated carbon dust 100--500mg, or ultrasonic and stirred for several all over after, at 60-80 DEG C, oil bath solvent evaporated, then puts into vacuum drying oven 60-80 DEG C of dry 8-10 h, takes out and grind and put into tube furnace after drying completes, under nitrogen atmosphere, 120-180 DEG C of process 3-5h.Then spend deionized water 1-3 time, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; Wherein the mol ratio of natrium citricum and the total metal of presoma is 1:1-5:1; Wherein presoma is by the one in ruthenic chloride, palladium bichloride, iridium chloride or two or morely to form;
In above-mentioned preparation method, the active metal component that step (3) described electric depositing solution contains comprises: more than one in Pt, Au, Ir; Described shell metallic salt comprise in dichloro four ammino platinum, chloroplatinic acid, gold chloride, iridous chloride more than one; 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 contains 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) ratio different according to the difference of metal molar concentration in electrolyte, its value is 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 all shows good activity to the reduction of methanol oxidation, Oxidation of Formic Acid and oxygen, can be used as hydrogen-oxygen fuel cell, DMFC, the anode of direct methanoic acid fuel cell and cathod catalyst, 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 kind of catalyst also can be used as hydrogenation on chemical industry and oxidation catalyst.
The present invention can also use the core of carbon-supported metal nano particle as nucleocapsid catalyst of business.
Compared with prior art, fuel cell catalyst with core-casing structure material of the present invention and preparation method thereof tool has the following advantages:
(1) shell thickness of fuel cell catalyst with core-casing structure of the present invention can be as thin as 0.5-2.0 nm, and the size of core-shell structure nanometer particle can be as small as 3-5 nm, effectively can improve platinum utilization, reduces its use amount.
(2) impulse electrodeposition technology proposed by the invention compared with prior art comparatively, except have easy and simple to handle, easily realize except the advantage of large-scale industrial production, and after the scan round created before deposition under negative potential short-term shelve the pretreatment operation on reducing electrode surface, realize the activation to substrate catalyst nanoparticle surface and reduction; To be beneficial in subsequent step shell metallic in the deposition of substrate catalyst nanoparticle surface, thus the chemical property of current efficiency when substantially increasing deposition and deposition rear catalyst.
(3) catalyst obtained by 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 activity comparable commodity Pt/C catalyst of unit mass platinum improves 2-10 doubly;
(4) catalyst with core-casing structure obtained by the present invention has good stability.
(5) carbon that the present invention obtains carries catalyst with core-casing structure, has the catalytic activity to methanol oxidation and the catalytic activity for hydrogen reduction that exceed several times than business Pt/C catalyst.
(6) used in the present invention high pressure organic sol method employing natrium citricum is complexing agent, ethylene glycol is solvent and reducing agent, in order to accelerate the rate of dissolution of natrium citricum in solvent ethylene glycol, have employed the way of grinding natrium citricum, accelerate natrium citricum rate of dissolution in a solvent greatly, effectively shorten experiment consuming time, simplify experimental procedure, reduce energy consumption greatly.
Accompanying drawing explanation
High-resolution-ration transmission electric-lens (HRTEM) figure of the catalyst with core-casing structure Ru@Pt/C of Fig. 1 obtained by embodiment 1.
High angle annular dark field scanning transmission electron microscope (HAADF-STEM) figure of the catalyst with core-casing structure Ru@Pt/C of Fig. 2 obtained by embodiment 1.
Fig. 3 is embodiment 1 and the methanol oxidation apparent activity figure of catalyst in comparative example 1,2,3.
Fig. 4 is embodiment 1 and current density (in mA/ug.Pt) block diagram under the methanol oxidation spike potential of catalyst in comparative example 1,2,3.
The catalyst with core-casing structure Ru@Pt/C of Fig. 5 obtained by embodiment 1 and comparative example 3 commercial catalysts are to methanol oxidation stability test figure.
Fig. 6 is embodiment 1 and the hydrogen reduction apparent activity figure of catalyst in comparative example 1,2,3.
Fig. 7 is embodiment 1 and hydrogen reduction current density (in mA/ug.Pt) block diagram under 0.6 V (reference is the Ag/AgCl electrode of 3M) current potential of catalyst in comparative example 1,2,3.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further illustrated, and following examples are only used to 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) 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 500 mL acetone stirred at ambient temperature 8 h to remove oxide in carbon dust and organic impurities, filter also with intermediate water washing, then vacuum drying at 70 DEG C; Dried carbon dust is transferred to tube furnace, and lower 500 DEG C of roasting 2 h of nitrogen atmosphere protection are with impurity such as organics removal; Carbon dust is transferred in 500 mL there-necked flasks afterwards, add 200 mL 10% HNO
3with 100 mL 30% H
2o
2mixed liquor, adds hot reflux 6 h at 80 DEG C, and filter and wash to neutrality with intermediate water, in 80 DEG C of baking ovens, vacuum drying 12 h, grinds for subsequent use.
(B) high pressure organic sol method prepares 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 carbon dust that 155.4 mg are pretreated, between or ultrasonic and stirred for several all over after, add KOH/ ethylene glycol solution and regulate more than pH to 10, proceed in the autoclave being lined with tetrafluoroethene liner, put into 180 DEG C, baking oven reaction, 8 h, react and after being cooled to room temperature, added rare HNO
3adjust below pH to 5.Then spend deionized water 3-5 time, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h.
(2) constant current impulse method is adopted to prepare Ru@Pt/C:
5 mg Ru/C add 2 mL and contain in the aqueous isopropanol of perfluorinated sulfonic resin (Nafion) of 0.15 wt%, after ultrasonic one-tenth prepared Chinese ink shape slurry, get 5 uL slurries and are evenly coated on the glass-carbon electrode as working electrode matrix, and dry under infrared lamp;
Working electrode is placed in the 0.1 M HClO that nitrogen is saturated
4in solution, sweep to-0.2 V with the speed of sweeping of 50 mV/s from open-circuit voltage, after 20 circles, under the current potential of-0.2 V, suspend 3min.
Then working electrode is proceeded to rapidly the saturated shell metallic salting liquid of nitrogen (dichloro four ammino platinum, concentration is 50 mM, containing the sodium sulphate of 0.1 M, the natrium citricum of 0.125 M), adopt platinum filament and Ag/AgCl electrode respectively as to electrode and reference electrode, according to the constant current pulsed deposition program preset, (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, and electrodeposition temperature is room temperature), obtain Ru@Pt/C core-shell structure catalyst, theoretical platinum carrying capacity is 2.3 wt%.
The actual composition of catalyst is determined by atomic absorption spectrum.Specific practice is: washed out from electrode surface by catalyst ethanol, then add aqua regia dissolution, and finally preparation becomes certain density solution, determines its concentration with atomic absorption spectrum, and finally converting 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 dark field scanning transmission electron microscope (HAADF-STEM) to observe the nucleocapsid structure of catalyst nanoparticles.
As can be seen from Fig. 1 and Fig. 2, the average grain diameter of this catalyst at about 5 nm (Fig. 1), and defines the Pt shell (Fig. 2) of one deck 1-2 about nm.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 two kinds of different metals respectively; Can the shell metallic of more figuratively bright employing impulse method deposition be coated on core metallic circumferential from two-part intensity, instead of form alloy, independent particle neither be defined, peripheral compared with highlights divide have 1-2nm to illustrate that shell is 1-2nm is 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, carry out cyclic voltammetry scan with the speed of sweeping of 50 mV/s, determine the catalytic activity that catalyst is oxidized for Methanol Anode, the results are shown in Table 1 hurdle 1;
(C) O_2 cathodic reduction catalytic performance test:
Adopt three-electrode system, at the 0.1 M HClO that oxygen is saturated
4in, sweep speed with 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.
Unless otherwise indicated, catalyst involved in the present invention is all identical with above method of testing for the method for testing of the activity of the cathodic reduction of methyl alcohol/formic acid anodic oxidation 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) article (A) in embodiment 1.
(2) Pt/C-P preparation: except the Ru/C adopting blank carbon dust to replace in embodiment 1, described in (2) article 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 deposition legal system to be designated as Ru@Pt/C-D for Ru@Pt/C():
(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 instead of the pulsed deposition of embodiment 1, depositing current density is 3 mA/cm
2, sedimentation time is 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.
Find out from Fig. 3, in embodiment 1 and catalyst in comparative example 1,2,3, except comparative example 1, the apparent activity of catalyst that obtains of Direct precipitation is the poorest on the carbon carrier, the apparent activity of other several catalyst is more or less the same, cause the reason of this phenomenon be be not converted to unit mass Pt on active, within the specific limits, better containing the apparent activity that Pt amount is many.
Different catalysts mass ratio in comparison diagram 4 is active, can know and draw, the catalyst adopting embodiment 1 pulsed deposition process to prepare has the highest activity on the Pt of unit mass (ug), thus illustrates that pulsed deposition has obvious advantage.But directly pulsed deposition but obtains very poor performance on the carbon carrier, thus the effect that core metal plays in the catalyst is described, thus illustrates that catalyst with core-casing structure has obvious advantage.
As can be seen from Figure 5, the catalyst with core-casing structure adopting embodiment 1 pulse electrodeposition to prepare has extraordinary stability, and after the circulation of 2000 circles, its performance only reduces 5%; And comparative example 3 commercial catalysts just has serious decay in front 20 circles, to its performance degradation 50% during 1000 circle.
Composition graphs 6 and Fig. 7, can obtain the conclusion identical with methanol oxidation: the catalyst 1, adopting pulsed deposition process to prepare has the highest oxygen reduction activity on the Pt of unit mass (ug), thus illustrate that pulsed deposition has obvious advantage.2, directly pulsed deposition but obtains very poor performance on the carbon carrier, thus the effect that core metal plays in the catalyst is described, thus illustrates that 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) constant current impulse method is adopted to prepare Ru@Pt/C:
Except as follows except listed 2, the other the same as in Example 1
(A) shell metallic salting liquid (chloroplatinic acid, concentration 50 mM, containing 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 turn-off time is 0.5 ms, and umber of pulse is 1300.
(C) platinum content of catalyst is 2.5 wt%.
(3) catalyst performance test and sign are with embodiment 1, the results are shown in Table 1 hurdle 2.
embodiment 3:Ir@Pt/CNTs catalyst
Replace XC-72R carbon black divided by CNT, replace outside ruthenium trichloride with iridous chloride, other preparation and method of testing completely identical with embodiment 1, the results are shown in Table 1 hurdle 3.
embodiment 4:Ru@Pt/rGO catalyst
Except some difference following, 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, containing 0.1 M sodium sulphate, 0.125 M EDTA);
(3) pulse current is 5 mA/cm
2, the admittance time is 0.1 ms, and turn-off time is 1.5 ms;
(4) Pt theoretical deposition amount is 2%.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 4.
embodiment 5:RuAu@Pt/C catalyst
(1) as the preparation of the RuAu/C of core:
RuAu/C catalyst is obtained by sodium borohydride reduction.
First, take 22 mg polyvinyl alcohol, add 100 mL deionized waters, dissolve in 90 DEG C of heating water baths.Then precursor water solution is added---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 prepare sodium borohydride solution with frozen water, 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, spend deionized water, and be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h.
(2) constant current impulse method is adopted to prepare RuAu@Pt/C: with embodiment 4.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 5.
embodiment 6:IrCo@Pt/C catalyst
(1) as the preparation of the IrCo/C of core: instead of ruthenium trichloride solution with the mixed solution of cobalt nitrate and iridous chloride; Metal ion total concentration is constant; Other are with embodiment 1.
(2) constant current impulse method is adopted to prepare IrCo@Pt/C: except some difference following, the other the same as in Example 1
(A) shell metallic salting liquid (dichloro four ammino platinum, concentration 5 mM, containing 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, and turn-off time is 1.5 ms
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 6.
embodiment 7:RhRu@Pt/C catalyst
(1) as the preparation of the RhRu/C of core: instead of ruthenium trichloride solution with the mixed solution of radium chloride and ruthenic chloride; Metal ion total concentration is constant, the other the same as in Example 1;
(2) constant current impulse method is adopted to prepare RhRu@Pt/C: with embodiment 1
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 7.
embodiment 8:IrPd@AuPt/C catalyst
Except some difference following, the other the same as in Example 1;
(1) infusion process preparation is adopted 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 carbon dust that 100 mg are pretreated, between or ultrasonic and stirred for several all over after, at 70 DEG C, oil bath solvent evaporated, then vacuum drying oven 70 DEG C of drying 10 h are put into, take out after drying completes and grind and put into tube furnace, under nitrogen atmosphere, 180 DEG C of process 3 h.Then spend deionized water 2 times, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h;
(2) constant current impulse method is adopted 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, and electroplate liquid (is just changed to chlorauric acid solution by the concrete electro-deposition shell metallic Pt part implemented with 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 implemented with embodiment 1.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 8.
embodiment 9:IrNi@AuPt/C catalyst
Except some difference following, the other the same as in Example 1;
(1) as the preparation of the IrNi/C of core: instead of ruthenium trichloride solution with the mixed solution of iridous chloride and nickel acetate, metal ion total concentration is constant;
(2) constant current impulse method is adopted 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 implemented with embodiment 8; Then continue to adopt constant current pulse method to prepare IrNi@AuPt/C, the concrete electro-deposition shell metallic Pt part implemented with embodiment 1.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 9.
embodiment 10:Ru@Pt/C catalyst
Except some difference following, the other the same as in Example 1;
(1) the support electrode Ti electrode for the preparation of working electrode is replaced glassy carbon electrode.
(2) adhesive ptfe emulsion is replaced perfluorinated sulfonic resin by employing, and isopropyl alcohol replaced by solvent ethanol, and the concentration of resin changes 0.25% into.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 10.
embodiment 11:Ru@Pt/C catalyst
Except some difference following, the other the same as in Example 1;
(1) the support electrode platinum electrode for the preparation of working electrode is replaced glassy carbon electrode.
(2) adhesive fluorocarbon resin is replaced perfluorinated sulfonic resin by employing, and isopropyl alcohol replaced by solvent ethanol, and the concentration of resin changes 0.5% into.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 11.
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 for electro-deposition containing shell metallic working solution in, under stirring state, touch cathode base substrate catalyst formed working electrode.
Catalyst test and sign, with embodiment 1, the results are shown in Table 1 hurdle 12.
Data as can be seen from table 1, adopt the catalyst with nucleocapsid structure prepared of impulse method no matter active at the methanol oxidative activity of anode, Oxidation of Formic Acid, should Pt/C catalyst all than business 40% in the oxygen reduction activity of negative electrode will, be core taking Ru as core or Ir, when Pt is shell, the methanol oxidation Performance comparision of catalyst performance is excellent; And its hydrogen reduction performance take Ir as core, when Pt is shell, performance is best; When with Pd and other metal alloys for core time, it is active that catalyst shows better Oxidation of Formic Acid.When with Ir, Pd alloy for core, when Au, Pt are shell, the catalyst of this special construction no matter show be the hydrogen reduction performance of anode methyl alcohol or Oxidation of Formic Acid or negative electrode, this kind of catalyst is one best in all catalyst.
The anode methyl alcohol of catalyst obtained by each embodiment of table 1 or Oxidation of Formic Acid performance and cathodic oxygen reduction performance summary sheet
Claims (7)
1. a pulse electrodeposition preparation method for fuel cell catalyst with core-casing structure, is characterized in that, comprises the following steps:
(1) the carbon carrier carried metal as core or alloy nano particle is prepared: first carbon carrier is carried out pretreatment, after using as the metal simple-substance of core or alloy nanometer particle load on the carbon carrier, obtain the carbon carrier carried metal simple substance as core or alloy nano particle, i.e. substrate catalyst; Described metal simple-substance comprises Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described alloy comprises by the bianry alloy of two kinds of compositions any in Ru, Pd, Rh, Ir, Ag, Au, Co or Ni or the ternary alloy three-partalloy by three kinds of compositions any in Ru, Pd, Rh, Ir, Ag, Au, Co or Ni; Described carbon carrier comprises XC-72R carbon black, CNT, Graphene; Metal simple-substance or alloy nano particle load capacity is on the carbon carrier 10wt%-40wt%, and the size of nano particle is 1-10 nm; Describedly using as the metal simple-substance of core or the nanometer particle load method on the carbon carrier of alloy be: impregnation-reduction method, 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, and add in the alcohol solution containing adhesive, ultrasonic disperse makes catalyst pulp, gets catalyst pulp and is coated in surface as working electrode matrix, namely obtain the working electrode for pulse electrodeposition after drying; Described adhesive comprises ptfe emulsion, perfluorinated sulfonic resin emulsion or fluorocarbon resin emulsion, and use amount mass percent is the 1%-30% accounting for 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 platinum plating titanium sheet; The mode of described drying is irradiated dry in dry, baking oven under comprising infrared lamp or natural air drying is dry;
Method two is: substrate catalyst is directly added for electro-deposition containing in the working solution of shell metallic, under stirring condition, the substrate catalyst of Contact cathod matrix forms working electrode;
(3) pulse electrodeposition, is placed in the 0.1 M HClO that nitrogen is saturated by the working electrode made
4in solution, sweep to-0.3 ~-0.2 V with the speed of sweeping of 50 mV/s from open-circuit voltage, under the current potential of-0.3 ~-0.2 V, suspend 2-4 min after 20 circles, realize the activation to substrate catalyst nanoparticle surface and reduction; After activation and reduction complete, rapidly electrode is proceeded in the saturated electric depositing solution containing shell metallic salt, complexing agent, conductive auxiliary agent of nitrogen, insert auxiliary electrode and reference electrode; Setting pulse frequency, admittance and turn-off time, pulsed deposition total time, then start pulse electrodeposition, electro-deposition completes, i.e. obtained a kind of fuel cell catalyst with core-casing structure; Described pulse frequency is 100 – 10000 s
-1, each packet of pulses contains 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) ratio different according to the difference of metal molar concentration in electrolyte, its value is between 0.1-100; Total umber of pulse is 100-2000.
2. the pulse electrodeposition preparation method of fuel cell catalyst with core-casing structure according to claim 1, it is characterized in that, describedly carbon carrier is carried out pretreatment be specially: take 5-20 g carbon carrier, add 200-1000 mL acetone stirred at ambient temperature 6-10 h, filter, washing, then vacuum drying at 60-70 DEG C; By dried carbon dust 250-500 DEG C 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 DEG C, and filter and wash to neutrality with intermediate water, in 60-80 DEG C of baking oven, vacuum drying 8-24 h, grinds for subsequent use, obtains pretreated carbon carrier;
Described high pressure organic sol method is specially: add in the ethylene glycol solution of presoma after being ground by natrium citricum, abundant stirring, ultrasonic natrium citricum is dissolved rapidly after add pretreated carbon carrier 100--500mg, between or ultrasonic and stirred for several all over after, add KOH/ ethylene glycol solution and regulate more than pH to 10, proceed in the autoclave being lined with tetrafluoroethene liner, put into baking oven 120-180 DEG C of reaction 8-10 h, reacted and after being cooled to room temperature, added rare HNO
3adjust below pH to 5, then spend deionized water 3-5 time, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; Wherein in natrium citricum and presoma, the mol ratio of total metal is 1:1-5:1, and wherein presoma comprises more than one less than three kinds in ruthenic chloride, palladium bichloride, gold chloride, iridium chloride, silver nitrate, cobalt nitrate, cobalt acetate, nickel acetate and radium chloride; 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, dissolve in heating water bath, then add precursor water solution, after stirring, prepare sodium borohydride aqueous solution with frozen water, be dropwise added drop-wise in precursor water solution, stir, add carbon dust 100--500mg, stir 6-10 h, spend deionized water, and be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; 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 impregnation-reduction method is specially: natrium citricum is added precursor water solution, stir, add pretreated carbon dust 100--500mg, between or ultrasonic and stirred for several all over after, at 60-80 DEG C, oil bath solvent evaporated, then vacuum drying oven 60-80 DEG C of dry 8-10 h is put into, take out after drying completes and grind and put into tube furnace, under nitrogen atmosphere, 120-180 DEG C of process 3-5h;
Then spend deionized water 1-3 time, be placed in vacuum drying chamber 70 DEG C of vacuum drying 12 h; Wherein the mol ratio of natrium citricum and the total metal of presoma is 1:1-5:1; Wherein presoma is by the one in ruthenic chloride, palladium bichloride, iridium chloride or two or morely to form.
3. the pulse electrodeposition preparation method of fuel cell catalyst with core-casing structure according to claim 1, is characterized in that, the active metal component that step (3) described electric depositing solution contains comprises: more than one in Pt, Au, Ir; Described shell metallic salt comprise in dichloro four ammino platinum, chloroplatinic acid, gold chloride, iridous chloride more than one; 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 fuel cell catalyst with core-casing structure according to claim 1, is characterized in that the pulse current density of pulse electrodeposition in step (3) is 1-10 mA/cm
2.
5. the fuel cell catalyst with core-casing structure prepared by preparation method according to 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 coated on carbon carrier carried metal simple substance as core or alloy nanoparticle sub-surface using the form of ultra-thin shell; Wherein, the ternary alloy three-partalloy that nano particle as core comprises non-platinum noble metals, transition metal, the bianry alloy be made up of two kinds of metals any in non-platinum noble metals and transition metal or is made up of three kinds of metals any in non-platinum noble metals and transition metal, the size of the nano particle of core is at 1-10 nm; Active metal as shell comprises Pt, Ir, Au or by two or three alloy formed 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%.
6. fuel cell catalyst with core-casing structure according to claim 5, is characterized in that: described ultra-thin shell is made up 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.
7. fuel cell catalyst with core-casing structure according to claim 5, it is characterized in that: described catalyst all shows good activity to the reduction of methanol oxidation, Oxidation of Formic Acid and oxygen, can be used as hydrogen-oxygen fuel cell, DMFC, the anode of direct methanoic acid fuel cell and cathod catalyst, 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 kind of catalyst is also as the hydrogenation on chemical industry and oxidation catalyst.
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