CN105680054A - Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell - Google Patents
Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell Download PDFInfo
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- CN105680054A CN105680054A CN201410652962.5A CN201410652962A CN105680054A CN 105680054 A CN105680054 A CN 105680054A CN 201410652962 A CN201410652962 A CN 201410652962A CN 105680054 A CN105680054 A CN 105680054A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method for a supported hollow-structured alloy catalyst for a low-temperature fuel cell. The preparation method specifically comprises the steps of preparing supported transitional metal nanoparticles as a template in low-boiling-point water or ethyl alcohol in the absence of a surfactant; and enabling the template to be subjected to a replacement reaction with a noble metal salt solution so as to obtain the supported hollow-structured catalyst with relatively uniform grain diameters of 2-10nm. Tests prove that the oxygen reduction catalytic activity of the catalyst obtained by the invention is 3.9 times of that of commercialized catalysts; and therefore, the catalyst material obtained by the preparation method has great application potentials in proton exchange membrane fuel cells and direct methanol fuel cells.
Description
Technical field
The invention belongs to fuel cell field, be specifically related to a kind of low-temperature fuel cell preparation method with loaded hollow-core construction alloy catalyst.
Background technology
As a kind of clean energy resource converting apparatus, the sustainable development in the world will be made tremendous contribution by Proton Exchange Membrane Fuel Cells. The advantages such as Proton Exchange Membrane Fuel Cells has environmental friendliness, energy Transform efficiency is high, power density high, simple in construction and started quickly at low temperature, show good prospect in replacing gasoline engine, portable power supplies, the electrical source of power of the vehicles and stationary electric power plant. But, the commercialization of Proton Exchange Membrane Fuel Cells is faced with the high problem with poor stability of cost, and its holistic cost and performance are heavily dependent on the Cost And Performance of catalyst; Catalyst uses precious metals pt in a large number, and the resource-constrained of Pt, price is significantly high. In order to reduce the cost of fuel cell, it is necessary to reduce the consumption of Pt, this catalysis activity just requiring to improve unit mass Pt, especially the catalysis activity of cathodic oxygen reduction, is one reacts more slowly because the kinetics of hydrogen reduction determines it.
Relative to solid metal catalyst, the advantage that hollow-core construction shows low-density, high-specific surface area, saving material and low cost. Therefore, preparation hollow-core construction catalyst is one of effective ways improving unit mass Pt catalysis activity. With non-Pt metal for template, the hollow-core construction that preparation is shell with Pt alloy, it is possible to improve the utilization rate of Pt. It addition, by the interaction between two or three metal of shell, it is possible to the electronic structure of regulation and control Pt and geometry mechanism, and then improve the catalysis activity and selectivity of catalyst; Meanwhile, the surfaces externally and internally with pertusate hollow shell structure is respectively provided with catalytic action, can improve the Pt having catalytic action ratio in total Pt load amount, thus improving the utilization rate of Pt.
At present; liquid phase synthesis is prepared metal nanoparticle and is mostly carried out in the presence of various protective agents (polyvinylpyrrolidone, polyacrylic acid, ammonium salt cationoid surfactant, sulfonic acid and sulfuric acid based anion surfactant etc.), thus effectively controlling size and the pattern of metal nanoparticle.
It is template, cetyl trimethylammonium bromide is that Pt nano hollow structure prepared by protective agent that Chinese patent CN200910023865.9 discloses the cuprous oxide particle of a kind of method 50-1000nm.It is protective agent that Chinese patent CN200310114338.1 discloses a kind of method citric acid, and cobalt is the Pt nano hollow structure that template prepares that particle diameter is 15-50nm. It is carrier that Chinese patent CN201110298886.9 discloses a kind of method Graphene, and polyvinylpyrrolidone is protective agent, and nickel is the Pt nano hollow structure that particle diameter is 10-50nm that template prepares that Graphene supports. United States Patent (USP) 2012/0003563A1 discloses a kind of method Al or Mg or Zn powder is template, uses AgNO3Displacement obtains how dendritic silver nano-grain, then obtains how dendritic Pt nanoparticle with platinum salt displacement Ag. United States Patent (USP) 2013/0344421A1 discloses a kind of method reducing agent reduction transition metal and as template, then obtains hollow-core construction eelctro-catalyst with platinum salt displacement. The particle diameter of the Pt nanoparticle obtained is 3-20nm.
For fuel-cell catalyst, for obtaining high using rate of metal, catalyst nanoparticles should have less particle diameter, is generally less than 10nm; Meanwhile, uniform particle size distribution and dispersibility good on carrier thereof, also most important for obtaining high catalysis activity. Document (Yu; X.F.; etal.Highperformanceelectrocatalyst:Pt-Cuhollownanocryst als.ChemicalCommunications; 2011.47 (28): p.8094-8096.) report and utilize the Cu method preparing hollow Pt for template; having selected high boiling oleyl amine is solvent; cetrimonium bronmide is protective agent, utilizes hydro-thermal method to react 24h at 170 DEG C, and the nano particle diameter obtained is approximately 11.5nm.
Summary of the invention
Present invention aim at the preparation method proposing the porous hollow constructional alloy catalyst of the loaded height rough surface of a kind of low-temperature fuel cell, test finds, its oxygen reduction catalytic activity is 3.9 times of commercialized catalyst, adopts the catalyst material that this preparation method obtains to have huge application potential in Proton Exchange Membrane Fuel Cells and DMFC.
The present invention comprises the steps of
Comprise the following steps:
1) in low boiling point solvent, transition metal salt, stirring so that it is be completely dissolved, obtain transition metal salt solution are added;
2) adding carrier in above-mentioned solution, stirring, sonic oscillation make it be uniformly dispersed, and obtain suspension;
3) at 20-100 DEG C, to step 2) suspension passes into noble gas 1-6 hour, then in suspension, add reducing agent, stirring reaction 1-12 hour at 40-100 DEG C;
4) to step 3) solution that obtains adds water-soluble precious metal precursor, at 40-100 DEG C, stirring reaction 2-12 hour, is cooled to room temperature, centrifugal, washing, and vacuum drying obtains solid supported noble metal alloy catalyst;
5) taking above-mentioned catalyst to mix with acid solution, ultrasonic to being uniformly dispersed, at 20-100 DEG C, stirring reaction 6-24 hour, is cooled to room temperature, centrifugal, washing, and vacuum drying obtains loaded hollow-core construction metallic catalyst.
Step 1) in, low boiling point solvent is water or ethanol, and transition metal salt is one or more in the sulfate of Fe, Co, Ni, Cu, nitrate or halogenide, and the concentration of transition metal salt solution is 0.5-5mmol/L.
Carrier is activated carbon, CNT, Graphene, tungsten carbide or indium tin oxide.
Step 3) in, reducing agent is sodium borohydride or hydrazine hydrate; Noble gas is Ar or N2, the mol ratio of reducing agent and transition metal salt is 1:10-10:1.
Step 4) in, water-soluble precious metal precursor is one or more the sulfate in Pt, Pd, Ir, Ru, nitrate, halogenide, complex, halogen acids or halogen acid salt; Complex is platinum acetate and palladium.
Step 2) in addition and the step 4 of carrier) in water-soluble precious metal precursor the mass ratio of precious metal element gross mass be 1:4 to 4:1.
Step 4) in the amount of water-soluble precious metal presoma that adds make noble metal and step 1) atomic ratio of transition metal in transition metal salt is 10:1-1:10.
Step 5) in, acid solution is H2SO4Or HNO3Aqueous solution, acid concentration is 0.1-10mol/L.
Step 5) in, catalyst metals is the hollow-core construction of particle diameter 3.5-8.5nm, and mean diameter is 6-8nm.
Step 5) in, described loaded hollow-core construction metallic catalyst is the porous hollow structure catalyst that loaded apparent height is coarse.
Obtain loaded hollow-core construction metallic catalyst and be applied to low-temperature fuel cell.
Loaded hollow-core construction metallic catalyst is the porous hollow constructional alloy catalyst that a kind of loaded apparent height is coarse.
Present invention beneficial effect compared with the prior art
1. method provided by the invention is with the ethanol of cheap and easy to get, low boiling and small-molecular-weight or water for solvent, reduces catalyst preparing cost, makes the production process greenization of catalyst;
2. preparation process does not use the macromolecule organics such as surfactant, decrease and use the tedious steps needing repeatedly washing, high speed centrifugation just can obtain comparatively clean catalyst in synthesis of surfactant process, simplify the technological process of production further, reduce production cost;
3. preparation process carries out at a lower temperature, reduces the requirement to equipment corrosion resistance and heater;
4. the preparation method that the present invention adopts is simply effective, by being previously added carrier, and strictly control reactant concentration, reaction temperature and response time, the porous hollow constructional alloy catalyst of the loaded height rough surface prepared has less particle diameter and less particle size distribution, prepared catalyst there is good dispersibility on carrier, additionally, can be effectively improved platinum utilization simultaneously, reduce the consumption of platinum, oxygen reduction reaction is shown higher catalysis activity and stability;
5. test finds, its oxygen reduction catalytic activity is 3.9 times of commercialized catalyst, adopts the catalyst material that this preparation method obtains to have huge application potential in Proton Exchange Membrane Fuel Cells and DMFC.
Accompanying drawing explanation
Fig. 1 is the structural representation of the porous hollow structure C uPt nano-particle of the height rough surface of the embodiment of the present invention one preparation.
Fig. 2 is the porous hollow structure C u of the loaded height rough surface of the embodiment of the present invention one preparation2Pt1Nanoparticle (Cu2Pt1/ C) TEM photo. The porous hollow structure C u of height rough surface2Pt1The particle diameter of nanoparticle is mainly distributed between 3～7nm, and mean diameter is 5.17nm, and is uniformly dispersed on the carbon carrier.
Fig. 3 is the porous hollow structure C u of the loaded height rough surface of the embodiment of the present invention two preparation4Pt1The TEM photo of nanoparticle. The porous hollow structure C u of height rough surface4Pt1The particle diameter of nanoparticle is mainly distributed between 2～5nm, and mean diameter is 3.59nm, and is uniformly dispersed on the carbon carrier.
Fig. 4 is the porous hollow structure C u of the loaded height rough surface of the embodiment of the present invention three preparation1Pt1The TEM photo of nanoparticle.The porous hollow structure C u of height rough surface1Pt1The particle diameter of nanoparticle is mainly distributed between 3～9nm, and mean diameter is 5.16nm, and is uniformly dispersed on the carbon carrier.
Fig. 5 is the porous hollow structure C u of the loaded height rough surface of the embodiment of the present invention four preparation10Pt4Ir1The TEM photo of nanoparticle. The porous hollow structure C u of height rough surface10Pt4Ir1The particle diameter of nanoparticle is mainly distributed between 6～10nm, and mean diameter is 8.50nm, and is uniformly dispersed on the carbon carrier.
Fig. 6 is the porous hollow structure C u of the loaded height rough surface of the embodiment of the present invention five preparation8Pt3Ru1The TEM photo of nanoparticle. The porous hollow structure C u of height rough surface8Pt3Ru1The particle diameter of nanoparticle is mainly distributed between 3～7nm, and mean diameter is 4.96nm, and is uniformly dispersed on the carbon carrier.
Fig. 7 is the porous hollow structure C u of the height rough surface of the embodiment of the present invention one preparation2Pt1/ C and 20%Pt/C (JM) is cyclic voltammetry curve and polarization curves of oxygen reduction in rotating disk electrode (r.d.e) (RDE) is tested. Test result shows: Cu2Pt1The electrochemical surface area of/C is 23.4m2/ g, area specific activity is 882.7 μ A/cm2Pt, mass ratio activity is 207.0mA/mgPt; And the electrochemical surface area of commercialization 20%PtC (JM) is 81.9m2/ g, area specific activity is 130.9 μ A/cm2Pt, mass ratio activity is 107.2mA/mgPt. Cyclic voltammetry electrolyte is N2Saturated 0.1mol/LHClO4Aqueous solution, sweeps speed for 50mV/s. Polarization curves of oxygen reduction test electrolyte is O2Saturated 0.1mol/LHClO4Aqueous solution, sweeps speed for 10mV/s, and forward scan, RDE rotating speed is 1600rpm. Test all at room temperature carries out, and on electrode, metal load amount is 19.1 μ g/cm2。
Fig. 8 is the preparation technology flow chart of catalyst in the present invention.
Detailed description of the invention
Embodiment one
1. in there-necked flask, add the 10 of 30ml-3The CuCl of mol/L2Alcoholic solution, adds XC72R activated carbon 11.7mg, and sonic oscillation is uniform.
2. in above-mentioned solution, pass into N230min, puts into heating 10min in 70 DEG C of oil baths.
3. in above-mentioned solution, add sodium borohydride so that sodium borohydride and CuCl2Mol ratio be 5:1, stirring reaction 1h in 70 DEG C of oil baths.
4. in above-mentioned solution, add the K of the 19.1mmol/L of 590 μ L2PtCl4Aqueous solution so that the molar concentration of Pt element is 0.50mmol/L, stirs 3h at 70 DEG C, is cooled to room temperature.
5. by said mixture centrifugation, with deionized water wash 3～5 times, finally dry under 60 DEG C of vacuum, obtain loaded hollow Cu2Pt1Nanoparticle (Cu2Pt1/C)。
Fig. 2 is loaded hollow Cu2Pt1The TEM photo of nanoparticle.
Embodiment two
1. in there-necked flask, add the 10 of 30ml-3The CuCl of mol/L2Alcoholic solution, adds XC72R activated carbon 11.7mg, and sonic oscillation is uniform.
2. in above-mentioned solution, pass into N230min, puts into heating 10min in 70 DEG C of oil baths.
3. in above-mentioned solution, add sodium borohydride so that sodium borohydride and CuCl2Mol ratio be 5:1, stirring reaction 1h in 70 DEG C of oil baths.
4. in above-mentioned solution, add the K of the 19.1mmol/L of 590 μ L2PtCl4Aqueous solution so that the molar concentration of Pt element is 0.25mmol/L, stirs 3h at 70 DEG C, is cooled to room temperature.
5. by said mixture centrifugation, with deionized water wash 3～5 times, finally dry under 60 DEG C of vacuum, obtain loaded hollow Cu4Pt1Nanoparticle (Cu4Pt1/C)。
Fig. 3 is loaded hollow Cu4Pt1The TEM photo of nanoparticle.
Embodiment three
1. in there-necked flask, add the 10 of 30ml-3The CuCl of mol/L2Alcoholic solution, adds XC72R activated carbon 11.7mg, and sonic oscillation is uniform.
2. in above-mentioned solution, pass into N230min, puts into heating 10min in 70 DEG C of oil baths.
3. in above-mentioned solution, add sodium borohydride so that sodium borohydride and CuCl2Mol ratio be 5:1, stirring reaction 1h in 70 DEG C of oil baths.
4. in above-mentioned solution, add the K of the 19.1mmol/L of 590 μ L2PtCl4Aqueous solution so that the molar concentration of Pt element is 1.00mmol/L, stirs 3h at 70 DEG C, is cooled to room temperature.
5. by said mixture centrifugation, with deionized water wash 3～5 times, finally dry under 60 DEG C of vacuum, obtain loaded hollow Cu1Pt1Nanoparticle (Cu1Pt1/C)。
Fig. 4 is loaded hollow Cu1Pt1The TEM photo of nanoparticle.
Embodiment four
1. in there-necked flask, add the 10 of 30ml-3The CuCl of mol/L2Alcoholic solution, adds XC72R activated carbon 11.7mg, and sonic oscillation is uniform.
2. in above-mentioned solution, pass into N230min, puts into heating 10min in 70 DEG C of oil baths.
3. in above-mentioned solution, add sodium borohydride so that sodium borohydride and CuCl2Mol ratio be 5:1, stirring reaction 1h in 70 DEG C of oil baths.
4. in above-mentioned solution, add the K of 590 μ L2PtCl4Aqueous solution and H2IrCl6Aqueous solution so that the atomic ratio that molar concentration is 0.50mmol/L, Pt and Ir of Pt and Ir element sum is 4:1, stirs 3h at 70 DEG C, is cooled to room temperature.
5. by said mixture centrifugation, with deionized water wash 3～5 times, finally dry under 60 DEG C of vacuum, obtain loaded hollow Cu10Pt4Ir1Nanoparticle (Cu10Pt4Ir1/C)。
Fig. 5 is loaded hollow Cu10Pt4Ir1The TEM photo of nanoparticle.
Embodiment five
1. in there-necked flask, add the 10 of 30ml-3The CuCl of mol/L2Alcoholic solution, adds XC72R activated carbon 11.7mg, and sonic oscillation is uniform.
2. in above-mentioned solution, pass into N230min, puts into heating 10min in 70 DEG C of oil baths.
3. in above-mentioned solution, add sodium borohydride so that sodium borohydride and CuCl2Mol ratio be 5:1, stirring reaction 1h in 70 DEG C of oil baths.
4. in above-mentioned solution, add the K of 590 μ L2PtCl4Aqueous solution and RuCl3Aqueous solution so that the atomic ratio that molar concentration is 0.50mmol/L, Pt and Ru of Pt and Ru element sum is 3:1, stirs 3h at 70 DEG C, is cooled to room temperature.
5. by said mixture centrifugation, with deionized water wash 3～5 times, finally dry under 60 DEG C of vacuum, obtain loaded hollow Cu8Pt3Ru1Nanoparticle (Cu8Pt3Ru1/C)。
Fig. 6 is loaded hollow Cu8Pt3Ru1The TEM photo of nanoparticle.
Claims (9)
1. the low-temperature fuel cell preparation method of loaded hollow-core construction alloy catalyst, it is characterised in that comprise the following steps:
1) in low boiling point solvent, transition metal salt, stirring so that it is be completely dissolved, obtain transition metal salt solution are added;
2) adding carrier in above-mentioned solution, stirring, sonic oscillation make it be uniformly dispersed, and obtain suspension;
3) at 20-100 DEG C, to step 2) suspension passes into noble gas 1-6 hour, then in suspension, add reducing agent, stirring reaction 1-12 hour at 40-100 DEG C;
4) to step 3) solution that obtains adds water-soluble precious metal precursor, at 40-100 DEG C, stirring reaction 2-12 hour, is cooled to room temperature, centrifugal, washing, and vacuum drying obtains solid supported noble metal alloy catalyst;
5) step 4 is taken) catalyst that obtains mixes with acid solution, and ultrasonic to being uniformly dispersed, at 20-100 DEG C, stirring reaction 6-24 hour, is cooled to room temperature, centrifugal, washing, and vacuum drying obtains loaded hollow-core construction alloy catalyst.
2. preparation method according to claim 1, it is characterized in that, step 1) in, low boiling point solvent is water or ethanol, transition metal salt is one or more in the sulfate of Fe, Co, Ni, Cu, nitrate or halogenide, and the concentration of transition metal salt solution is 0.5-5mmol/L.
3. preparation method according to claim 1, it is characterised in that step 2) in, carrier is activated carbon, CNT, Graphene, tungsten carbide or indium tin oxide.
4. preparation method according to claim 1, it is characterised in that step 3) in, reducing agent is sodium borohydride or hydrazine hydrate; Noble gas is Ar or N2; The mol ratio of reducing agent and transition metal salt is 1:10-10:1.
5. preparation method according to claim 1, it is characterised in that step 4) in, water-soluble precious metal precursor is one or more the sulfate in Pt, Pd, Ir, Ru, nitrate, halogenide, halogen acids or halogen acid salt.
6. preparation method according to claim 1, it is characterised in that step 2) in addition and the step 4 of carrier) in water-soluble precious metal precursor the mass ratio of precious metal element gross mass be 1:4 to 4:1.
7. preparation method according to claim 1, it is characterised in that step 4) in the amount of water-soluble precious metal presoma that adds make noble metal and step 1) atomic ratio of transition metal in transition metal salt is 10:1-1:10.
8. preparation method according to claim 1, it is characterised in that step 5) in, acid solution is H2SO4Or HNO3Aqueous solution, concentration is 0.1-10mol/L.
9. preparation method according to claim 1, it is characterised in that step 5) in, in described loaded hollow-core construction alloy catalyst, alloy particle diameter is 3.5-8.5nm.
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