CN100398211C - Nucleocapsid catalyst in use for fuel cell and preparation method - Google Patents
Nucleocapsid catalyst in use for fuel cell and preparation method Download PDFInfo
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Abstract
The present invention provides a nucleocapsid catalyst for fuel cells and the preparing method thereof. The present invention is characterized by the controllability of the size of the catalyst and the thickness of a catalyst layer with catalyzing effects. The metallic activity of metal with low standard electrode electric potential is higher than that of metal with high standard electrode electric potential, and thus, the simple substances of ions of the metal with high standard electrode potential are easily separated. Firstly, nanometer particles of metal with low standard electrode electric potential are prepared, and metal with high standard electrode electric potential is separated by the nanometer particles; the amount of the separated metal is controlled less than the amount required by a replacement reaction theory; thus, the separated metal is coated on the surface of the nanometer particle of the metal with low standard electrode electric potential to obtain the nucleocapsid catalyst. The nucleocapsid catalyst with various thicknesses of catalyst layers can be obtained through adjusting the dose ratio of the two kinds of metal; the particle diameter of the nucleocapsid catalyst can be controlled through controlling the particle diameter of the prepared nanometer particle of the metal with high metal activity. The nucleocapsid catalyst prepared by the method has the advantages of large active specific surface area and high catalyzing efficiency.
Description
Technical field
The invention belongs to a kind of nucleocapsid catalyst in use for fuel cell and preparation method thereof
Background technology
Agglomeration easily takes place in the no carrying metal particle of nano-scale, causes specific area to reduce.Therefore the catalyst that uses in the fuel cell is commonly solid supported noble metal catalyst, carries platinum, ruthenium etc. as carbon.Owing to these noble metal scarcity of resources, cost an arm and a leg, so must take suitable preparation method and production technology to reduce the particle size of catalyst, its particle diameter is evenly distributed, and the decentralization that increases catalyst prevents catalyst agglomeration, thereby improve activity of such catalysts and utilization rate.Domestic and international many researchers have attempted several different methods and have prepared solid supported noble metal catalyst.
US3,992,331 have introduced a kind of activated carbon platinum carried catalysis agent method for preparing high dispersive.This method changes into sulfurous acid platinum sodium (Na6[Pt (SO with chloroplatinic acid (H2PtCl6) earlier
3)
4]), just sulfurous acid platinum sodium converts Hydrogen to then, heats in air and boils, and discharges unnecessary sulfite ion, and the dry at a certain temperature black colloid that obtains platinum adds the platinum catalyst that carbon carrier absorption platinum colloid is made 1.5～2.5 nanometers.This method has been replaced chlorion with inferior sulfate radical, and eliminated trace chlorine and caused that the catalytic performance of catalyst descends, but this method operating process complexity, the preparation cost height.
US5,641,723 have introduced a kind of process for preparing supported metal catalyst by colloid method.This method adopts NR
4BR
3H is reducing metal salt in oxolane (THF), has prepared the nano level metal colloid that the particle diameter of multiple quaternary amine protection is evenly distributed, and adds the metallic colloid of various carriers absorption preparations then, obtains supported catalyst.This method is operated under the anhydrous and oxygen-free condition, uses a large amount of toxic solvents, and has a large amount of waste materials residual.
US5,068,161 has introduced the method that a kind of immersion reduction method prepares supported metal catalyst.This method joins platinum acid chloride solution and uses NaHCO
3Be adjusted in the carbon dust of alkalescence a large amount of CO
2After gas discharges,, feed N by adding reducing agent or direct filtration dryings such as formaldehyde, formic acid, hydrazine hydrate
2/ H
2The gaseous mixture high temperature reduction, thus loaded Pt/C catalyst obtained.[CN99112700.5, CN02118282.5] also introduced the method that a kind of immersion reduction method prepares supported catalyst, and different is that this method is finished in organic solvent or mixed solvent.The platinum grain diameter of immersion reduction method preparation is inhomogeneous, distributed more widely, especially particularly outstanding when high carrying capacity above using.
Amine K, et a1.J.Chen.Soc.Fara.Trans, 1995,91:4451 has introduced the method that a kind of ion-exchange prepares supported catalyst.This method is handled carrier carbon with oxidant, makes carbon surface that the functional group of many electronegative property be arranged, and utilizes the Coulomb attraction between positive and negative charge, with positively charged platinum amine complex ion [Pt (NH
3)
4 2+] be incorporated into the electronegative functional group place of carbon surface, restore platinum grain with reducing agent then, obtain loaded Pt/C catalyst.Because functional group's number of the electronegative property that carbon surface is introduced is limited, the platinum carrying capacity is difficult to reach more than 5%.
Wu Shihua etc., petrochemical industry, 187:361 has introduced vacuum sputtering and the metal vapors sedimentation prepares catalyst, but these two kinds of methods are all very high to the equipment requirement, are not suitable for a large amount of productions.
Summary of the invention
The purpose of this invention is to provide that a kind of specific area is big, good dispersion degree, catalytic activity and high a kind of nucleocapsid catalyst in use for fuel cell and the preparation method of utilization rate.
To achieve these goals, utilize the low metal of standard electrode EMF, its metal active is higher than the high metal of standard electrode EMF, and simple substance is separated out in easily that standard electrode EMF is high metal ion displacement.The low metal nanoparticle of preparation standard electrode potential at first, come out with its metal replacement that standard electrode EMF is high, control the amount that the amount that is displaced the metal that comes is less than the theoretical needs of displacement reaction, thereby the metallic cover that acquisition is replaced is at the nucleocapsid catalyst on the low metal nanoparticle surface of standard electrode EMF.By regulating the dosage ratio of two kinds of metals, obtain the nucleocapsid catalyst of various Catalytic Layer thickness; By the particle diameter of the high metal nanoparticle of the metal active of control preparation, the particle diameter of control catalyst with core-casing structure.
Technical scheme of the present invention is:
A kind of nucleocapsid catalyst is characterized in that this catalyst is the catalyst with core-casing structure that the low metal of metal active is wrapped in the high metal nanoparticle surface of metal active, preparation with the following method, and preparation process is:
Step 1, configuration mixed solution, in deionized water solvent, add surfactant, stir, add the high metal water soluble compound of metal active simultaneously, be made into mixed solution, the content of metal is 0.001～1 mol in the mixed solution, the content of surfactant is 0.001～1 mol, wherein, the mol ratio 0.1～10: 1 of surfactant and metal, solvent is the deionized water of electrical conductivity＞18 megaohms;
Step 3, in the high nano metal solution of metal active that step 2 makes, add the low metallic solution of metal active while stirring, stirred 0.5～20 hour, and obtained the catalyst with core-casing structure solution that the low metal of metal active is wrapped in the high metal nanoparticle surface of metal active;
Step 4, step 3 is obtained catalyst with core-casing structure solution suction filtration, and spend deionised water 3～5 times,, obtain non-supported nucleocapsid catalyst in 60～90 ℃ of vacuum drying; Perhaps obtain adding carrier in the catalyst with core-casing structure solution vigorous stirring 10～25 hours, suction filtration in step 3, and spend deionised water 3～5 times, in 60～90 ℃ of vacuum drying, obtain loaded nucleocapsid catalyst, wherein, carrier is 10: 1～100 with the metal quality ratio.
Wherein, the metal water soluble compound that described metal active is high comprises water-soluble halide, sulfate, nitrate and the phosphate of Fe, Co, Ni, Cu, Mn, Cr, Ti, V and Mo metal.
Described surfactant comprises that (general formula is R-SO to sulfonate
3Na, carbon number is between 8～20 among the R), (general formula is ROSO to sulfuric acid ester salt
3M, M is Na, K, N (CH in the formula
2CH
2OH)
3Carbon number is 8～18 in the carbochain), amine salt (according to the number of organic substituent on the nitrogen-atoms be divided into primary, the second month in a season, uncle, quaternary amine), citric acid and salt surfactant thereof, amino acid pattern and imidazoline type amphoteric surfactant, polyethylene glycol type, polyalcohol type and alkyl hydrosulfide type non-ionic surface active agent.
Described reducing agent is NaBH
4Or N
2H
2H
2O.
The metallic solution that described metal active is low comprises the aqueous solution of water soluble sulfate, nitrate, phosphate, network and thing, halide, carbonyls, halogen acids and the salt of Pt, Pd, Ru, Rh, Ir, Os, Au, Ag.
The carrier of described supported catalyst is the material of high-specific surface area, good conductivity, good stability, comprising: graphite, carbon black, CNT, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2And molecular sieve.
The dosage of the thickness of the active low metal integument of described catalyst with core-casing structure surface metal by regulating the low metal of the high metal of metal active and metal active is than control; When the dosage of the low metal of high metal of metal active and metal active when big, the thickness of the active low metal integument of catalyst with core-casing structure surface metal gets the small value; The particle diameter of catalyst with core-casing structure is controlled by the particle diameter of the high metal nanoparticle of metal active of preparation, and when the particle diameter of the high metal nanoparticle of metal active hour, the catalyst with core-casing structure particle diameter gets the small value.
The preparation method of nucleocapsid catalyst of the present invention, it comprises the steps:
Step 1, configuration mixed solution, in deionized water solvent, add surfactant, stir, add the high metal water soluble compound of metal active simultaneously, be made into mixed solution, the content of metal is 0.001～1 mol in the mixed solution, the content of surfactant is 0.001～1 mol, wherein, the mol ratio 0.1～10: 1 of surfactant and metal, solvent is the deionized water of electrical conductivity＞18 megaohms;
Step 3, in the high nano metal solution of metal active that step 2 makes, add the low metallic solution of metal active while stirring, stirred 0.5～20 hour, and obtained the catalyst with core-casing structure solution that the low metal of metal active is wrapped in the high metal nanoparticle surface of metal active;
Step 4, step 3 is obtained catalyst with core-casing structure solution suction filtration, and spend deionised water 3～5 times,, obtain non-supported nucleocapsid catalyst in 60～90 ℃ of vacuum drying; Perhaps obtain adding carrier in the catalyst with core-casing structure solution vigorous stirring 10～25 hours, suction filtration in step 3, and spend deionised water 3～5 times, in 60～90 ℃ of vacuum drying, obtain loaded nucleocapsid catalyst, wherein, carrier is 10: 1～100 with the metal quality ratio;
The metal water soluble compound that described metal active is high comprises water-soluble halide, sulfate, nitrate and the phosphate of Fe, Co, Ni, Cu, Mn, Cr, Ti, V and Mo metal; Described surfactant comprises that general formula is R-SO
3Na, sulfonate, the general formula of carbon number between 8～20 is ROSO among the R
3M, M is Na, K, N (CH in the formula
2CH
2OH)
3, carbon number is 8～18 sulfuric acid ester salt, amine salt, citric acid and salt surfactant thereof in the carbochain, amino acid pattern and imidazoline type amphoteric surfactant, polyethylene glycol type, polyalcohol type and alkyl hydrosulfide type non-ionic surface active agent; Described reducing agent is NaBH
4Or N
2H
2H
2O; The metallic solution that described activity is low comprises the aqueous solution of water soluble sulfate, nitrate, phosphate, network and thing, halide, carbonyls, halogen acids and the salt of Pt, Pd, Ru, Rh, Ir, Os, Au, Ag; The carrier of described supported catalyst is graphite, carbon black, CNT, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve.
Characteristics of the present invention are to utilize the difference of metal active height, the active high metal nanoparticle of preparation earlier, then that metal active is low metal cements out from its solution, and the noble metal that has obtained catalytic action is wrapped in the catalyst of the nucleocapsid structure of lowpriced metal surface.And the thickness of the noble metal of a catalytic action, by regulating the dosage ratio control of two kinds of metals; The particle diameter of nucleocapsid catalyst is by the particle diameter control of the high metal nanoparticle of the metal active of adjusting preparation.The catalyst of this nucleocapsid structure both can be used as no catalyst-loaded use, also can be deposited on the carriers such as carbon dust, CNT and use as supported catalyst.The present invention can improve the specific area of the noble metal of catalytic action greatly, better brings into play its catalytic action.
Description of drawings
Fig. 1 is the monocell polarization curve of embodiment 1 and comparative example 1;
Fig. 2 is the embodiment of the invention 1 transmission electron microscope picture;
Fig. 3 is the embodiment of the invention 2 transmission electron microscope pictures;
Fig. 1 illustrates that fuel cell output performance of the present invention is good, catalyst efficient height.
The specific embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing.
Embodiment 1
Get 500 milliliters of the diallyl dimethyl ammoniumchloride of 0.05 mol, add 500 milliliters of the nickel chloride solutions of 0.02 mol, electronic stirring 3 minutes, 300 rev/mins of rotating speeds.The NaBH that adds 0.1 mol
415 milliliters, stirred 5 minutes, and feed H
2Protection.The H that adds 0.01 mol
2PtCl
6100 milliliters of solution, electronic stirring 1 hour, 500 rev/mins of rotating speeds.Add 0.29 gram VulcanXC-72 carbon dust, electronic stirring 15 hours, 5000 rev/mins of rotating speeds filter and with deionized water rinsing 5 times, 80 ℃ of following vacuum drying.The carbon that makes carries that carbon and platinum mass ratio are 3: 2 in [nickel] (platinum) (nuclear of element representation nucleocapsid structure in the square brackets, the shell of the element representation nucleocapsid structure in the bracket) catalyst.The transmission electron microscope picture of its catalyst such as Fig. 2.
Comparative example 1
Getting the platinum carrying capacity is that (Johnson Matthey company produces quality 40%Pt/C catalyst, the average grain diameter of formed by catalytic active particles Pt is 3 nanometers, the Pt carrying capacity is a quality 40%) as anode and cathod catalyst, and carry out the monocell performance relatively as the catalyst of positive machine and negative electrode with the catalyst of getting embodiment one.
Monocell assembling and performance test.The carbon paper that adopts E-TEK company to produce is a diffusion layer, and carbon paper passes through 100 microns of quality 30%PTFE (polytetrafluoroethylene (PTFE)) hydrophobic treatment and thickness in advance.To the carbon paper of hydrophobic mistake, the platinum carrying capacity of anode and negative electrode is 0.4 milligram/centimetre with catalyst coated
2The Nafion212 film that adopts DuPont company to produce is a PEM, and it is quality 5%H that the Nafion212 film is immersed weight concentration
2O
2In, 80 ℃ of following heat treatment 1 hour is with deionized water rinsing 3 times; Immerse the H of 0.5 mol again
2SO
480 ℃ of following heat treatment is 1 hour in the solution; Deionized water is changed in 80 ℃ of following heat treatment 1 hour in deionized water then therebetween 3 times.The Nafion212 film that to handle then later is clipped in the middle of the carbon paper that is brushed with catalyst, 125 ℃ of hot pressing 90 seconds, and pressure is 0.2 MPa.Employing a side have parallel slot to graphite cake be collector plate, end plate is gold-plated corrosion resistant plate.Operating condition is: P
CO2=P
H2=O MPa, battery temperature are 60 ℃, and anode 100% humidification, humidification temperature are 70 ℃.
The monocell polarization curve of embodiment 1 and comparative example 1 is seen Fig. 1, illustrates that fuel cell output performance of the present invention is good, catalyst efficient height.
Get 500 milliliters of the natrium citricums of 0.02 mol, add 500 milliliters of the cobalt chloride solutions of 0.01 mol, electronic stirring 5 minutes, 500 rev/mins of rotating speeds.The NaBH that adds 0.1 mol
415 milliliters, stirred 5 minutes, and feed H
2Protection.The H that adds 0.01 mol
2PtCl
6100 milliliters of solution, electronic stirring 1 hour, 500 rev/mins of rotating speeds filter and with deionized water rinsing 5 times, 60 ℃ of following vacuum drying.[cobalt] (platinum) catalyst that makes.The transmission electron microscope picture of its catalyst such as Fig. 3
Embodiment 3
Get 500 milliliters of the sodium dodecyl sulfate solutions of 0.04 mol, add 500 milliliters of the ferrum sulfuricum oxydatum solutums of 0.01 mol, electronic stirring 4 minutes, 400 rev/mins of rotating speeds.The N that adds 0.1 mol
2H
2H
2The O40 milliliter stirred 5 minutes, and fed H
2Protection.The RuCl that adds 0.01 mol
3100 milliliters of solution, electronic stirring 1 hour, 500 rev/mins of rotating speeds.Add 0.404 gram VulcanXC-72 carbon dust, electronic stirring 15 hours, 5000 rev/mins of rotating speeds filter and with deionized water rinsing 5 times, 80 ℃ of following vacuum drying.The carbon that makes carries that carbon and ruthenium mass ratio are 4: 1 in [iron] (ruthenium) catalyst.
Claims (3)
1. the preparation method of a nucleocapsid catalyst is characterized in that, comprises the steps:
Step 1, configuration mixed solution, in deionized water solvent, add surfactant, stir, add the high metal water soluble compound of metal active simultaneously, be made into mixed solution, the content of metal is 0.001～1 mol in the mixed solution, the content of surfactant is 0.001～1 mol, wherein, mol ratio 0.1～1 0 of surfactant and metal: 1, solvent is the deionized water of electrical conductivity＞18 megaohms;
Step 2, in the mixed solution of step 1, add the reducing agent several 1～10 times, stir, and feed the H2 protection, make the high nano metal solution of metal active with respect to metal molar;
Step 3, in the high nano metal solution of metal active that step 2 makes, add the low metallic solution of metal active while stirring, stirred 0.5～20 hour, and obtained the catalyst with core-casing structure solution that the low metal of metal active is wrapped in the high metal nanoparticle surface of metal active;
Step 4, step 3 is obtained catalyst with core-casing structure solution suction filtration, and spend deionised water 3～5 times,, obtain non-supported nucleocapsid catalyst in 60～90 ℃ of vacuum drying; Perhaps obtain adding carrier in the catalyst with core-casing structure solution vigorous stirring 10～25 hours, suction filtration in step 3, and spend deionised water 3～5 times, in 60～90 ℃ of vacuum drying, obtain loaded nucleocapsid catalyst, wherein, carrier is 10: 1～100 with the metal quality ratio;
Wherein, the metal water soluble compound that described metal active is high comprises water-soluble halide, sulfate, nitrate and the phosphate of Fe, Co and Ni, Cu, Mn, Cr, Ti, V and Mo metal; Described surfactant comprises that general formula is R-SO
3Na, sulfonate, the general formula of carbon number between 8～20 is ROSO among the R
3M, M is Na, K, N (CH in the formula
2CH
2OH)
3, carbon number is 8～18 sulfuric acid ester salt, amine salt, citric acid and salt surfactant thereof in the carbochain, amino acid pattern and imidazoline type amphoteric surfactant, polyethylene glycol type, polyalcohol type and alkyl hydrosulfide type non-ionic surface active agent; Described reducing agent is NaBH
4Or N
2H
2H
2O; The metallic solution that described activity is low comprises the aqueous solution of water soluble sulfate, nitrate, phosphate, network and thing, halide, carbonyls, halogen acids and the salt of Pt, Pd, Ru, Rh, Ir, Os, Au, Ag; The carrier of described supported catalyst is graphite, carbon black, CNT, carbon fiber, C-SBA-15, fullerene, conducting polymer, Al
2O
3, SiO
2, MgO, TiO
2Or molecular sieve.
2. the preparation method of a kind of nucleocapsid catalyst as claimed in claim 1, the dosage of the thickness that it is characterized in that the active low metal integument of described catalyst with core-casing structure surface metal by regulating the low metal of the high metal of metal active and metal active is than control; When the dosage of the low metal of high metal of metal active and metal active when big, the thickness of the active low metal integument of catalyst with core-casing structure surface metal gets the small value; The particle diameter of catalyst with core-casing structure is controlled by the particle diameter of the high metal nanoparticle of metal active of preparation, and when the particle diameter of the high metal nanoparticle of metal active hour, the catalyst with core-casing structure particle diameter gets the small value.
3. the nucleocapsid catalyst of claim 1 or 2 preparation method preparation, it is characterized in that this catalyst is the catalyst with core-casing structure that the low metal of metal active is wrapped in the high metal nanoparticle surface of metal active, wherein, the metal that described metal active is high comprises Fe, Co, Ni, Cu, Mn, Cr, Ti, V and Mo; The metal that described metal active is low comprises Pt, Pd, Ru, Rh, Ir, Os, Au and Ag.
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