CN114400334A - Platinum-based alloy catalyst and preparation method and application thereof - Google Patents
Platinum-based alloy catalyst and preparation method and application thereof Download PDFInfo
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- CN114400334A CN114400334A CN202111613654.8A CN202111613654A CN114400334A CN 114400334 A CN114400334 A CN 114400334A CN 202111613654 A CN202111613654 A CN 202111613654A CN 114400334 A CN114400334 A CN 114400334A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 63
- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- 238000000034 method Methods 0.000 claims abstract description 69
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- 239000000843 powder Substances 0.000 claims abstract description 24
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- 239000000446 fuel Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
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- 238000004062 sedimentation Methods 0.000 description 5
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- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910019026 PtCr Inorganic materials 0.000 description 1
- 229910002836 PtFe Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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- Inert Electrodes (AREA)
Abstract
The invention discloses a platinum-based alloy catalyst and a preparation method and application thereof, wherein the preparation method of the platinum-based alloy catalyst comprises the following steps: (1) mechanically grinding and mixing a Pt/C carrier, a metal precursor and deionized water according to a certain proportion, and quickly freezing and molding at (-200) - (-100) DEG C to obtain a solid mixture; (2) transferring or in-situ freeze drying the solid mixture obtained in the step (1) to obtain solid powder; (3) and (3) carrying out rapid heating sintering treatment on the solid powder in the step (2) in a reducing atmosphere, and then rapidly cooling to room temperature to obtain a final catalyst product. The preparation method of the platinum-based alloy catalyst has the characteristics of simplicity, convenient operation, easy industrial production and the like, can reduce working procedures to a certain extent and shorten process time, and the obtained catalyst material has activity superior to that of a commercial catalyst and can be applied to catalytic reaction in a fuel cell.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and electrocatalysis, and particularly relates to a platinum-based alloy catalyst and a preparation method and application thereof.
Background
Catalysts are one of the key materials within fuel cells. In order to improve the activity of the catalyst such as oxygen reduction (ORR) and Hydrogen Oxidation (HOR) and to reduce the amount of Pt used, a series of PtM/C alloy catalysts have been the focus of research. The PtM/C alloy catalyst is formed by doping other transition metals on the basis of Pt/C to form binary or multi-element alloy. In recent years, many researches on the catalysts are reported, and mainly include PtCo/C, PtCr/C, PtNi/C, PtFe/C and PtCe/C multi-element alloy catalysts which show better catalytic performance than pure Pt catalysts. Compared with the traditional Pt/C catalyst, the Pt-based alloy catalyst has the advantages that the Pt catalytic activity is improved and the dosage of platinum is reduced through the interaction with 3d transition metal electrons, such as ligand effect, stress effect and geometric effect.
In view of the great application value of the alloy catalyst, various methods for preparing the catalyst have been developed, and the most common methods are an impregnation method, a chemical reduction method, an ion exchange method, a colloid method, a microwave-promoted reduction method, an electrochemical method, a displacement method, a core-shell method, and the like. The traditional preparation method of the supported alloy catalyst comprises an impregnation method, a liquid phase reduction method, a common freeze drying method, a colloid method, a precipitation method and the like. Wherein: the common freeze-drying method is the most common and convenient method for preparing the supported catalyst, and comprises two parts: firstly, a precursor of an active center is uniformly mixed and dispersed with a carrier material in a solution system, then a catalyst precursor is obtained by volatilizing a solvent under the condition of low temperature, and the precursor is reduced at a proper temperature to form tiny particles to be loaded on the surface of the carrier. For example, after uniformly mixing cobalt salt, a platinum-carbon catalyst and a volatile solvent, the temperature is reduced to (-70) - (-20) DEG C within 2h for pre-freezing, then the platinum-cobalt precursor is obtained by vacuum freeze drying within the range of (-50) -80 ℃, the platinum-cobalt precursor is reduced at the temperature of 200-400 ℃ for 1-6h under the reducing atmosphere, and then the platinum-cobalt alloy catalyst is obtained by high-temperature heat treatment at the temperature of 500-900 ℃ for 1-3h under the reducing atmosphere. The method is simple to operate, but in the freezing process, the phenomena of coagulation and agglomeration exist among metal elements due to long time, the prepared metal elements are not uniformly distributed, and the particle size distribution is wide. For another example, a carbon support is added to an aqueous solution of a platinum-containing precursor compound and a transition metal-containing precursor compound; and adjusting the pH value by strong alkali in ice bath, quickly freezing within 2min, carrying out freeze drying treatment, finally carrying out heat treatment on the powder for more than 6h in a reducing atmosphere, and washing and drying to obtain the catalyst product. The prepared catalyst has good alloy state. The method can well control the particle size of the product, but the method deposits metal ions on the surface of a carrier by adding strong base for adjusting pH near the freezing point, and then removes introduced impurities and easily dissolved transition metals through the steps of washing, suction filtration, vacuum drying and the like, the process is complex and tedious, the use of a regulator has certain influence on the performance of a catalyst at the later stage, the method is particularly not favorable for the durability of the catalyst, and the content of the supported platinum is low.
The inventor finds that the impregnation method and the common freeze-drying method volatilize the solvent by means of high-temperature or low-temperature freeze-drying, the process is easy to generate sedimentation and delamination of metal ions, the metal distribution is not uniform after sintering, and the prepared metal particles have a wider size distribution due to the agglomeration phenomenon among particles under the condition of higher loading capacity. The liquid phase reduction method usually requires higher temperature and pressure, the process conditions are harsh, and the physical properties and catalytic activity of the finished catalyst are easily affected by the change of the reaction conditions. The colloid method has complex preparation process, more reaction steps and difficult removal of reaction auxiliary agent, and is not suitable for large-scale production. Precipitation methods load metal ions on a carrier by adjusting the pH of the solution system, and the addition of strong alkaline solutions may result in too high a local concentration, agglomeration, or lack of uniformity in composition. In addition, the batch production technology of the catalyst is not mature at present, which seriously restricts the autonomous controllable development of the hydrogen fuel cell industry in China.
Therefore, optimizing the preparation method of the Pt-based catalyst and developing the batch preparation process of the Pt-based catalyst are the research directions of the catalyst which is the key material of the PEMFC (proton exchange membrane fuel cell).
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a platinum-based alloy catalyst, in which a metal precursor, a Pt/C carrier, etc. are uniformly mixed in a certain proportion, then the mixed slurry is rapidly frozen and vacuum-dried in a low-temperature and extremely-cold atmosphere, and finally, a supported platinum-based alloy catalyst is obtained through the subsequent steps of high-temperature sintering, etc., the whole method has the characteristics of simplicity, convenient operation, easy industrial production, etc., and can reduce the number of processes to a certain extent and shorten the process time, and the obtained catalyst material has activity superior to that of a commercial catalyst, and can be applied to catalytic reaction in a fuel cell.
Another object of the present invention is to propose a platinum-based alloy catalyst.
It is a further object of the present invention to propose the use of a platinum-based alloy catalyst in a fuel cell.
To this end, an embodiment of the first aspect of the present application proposes a method for preparing a platinum-based alloy catalyst, comprising the steps of:
(1) mechanically grinding and mixing a Pt/C carrier, a metal precursor and deionized water according to a certain proportion, and quickly freezing and molding at (-200) - (-100) DEG C to obtain a solid mixture;
(2) transferring or in-situ freeze drying the solid mixture obtained in the step (1) to obtain solid powder;
(3) and (3) carrying out rapid heating sintering treatment on the solid powder in the step (2) in a reducing atmosphere, and then rapidly cooling to room temperature to obtain a final catalyst product.
In the step (1), the temperature for the rapid freeze forming is between (-200) - (-100) DEG C, and at the temperature, the rapid confinement of the metal ions on the Pt/C carrier can be realized, and the structure of the carbon carrier is not damaged, so that the activity and the durability of the catalyst product are not influenced.
In addition, the preparation method of the platinum-based alloy catalyst according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, in the step (1), the loading amount of Pt in the Pt/C carrier is 5-60 wt%, the particle size of Pt is 2-6nm, and C in the Pt/C carrier is one or more of carbon fiber, carbon nanotube, graphene, highly graphitized carbon, and carbon black.
In some embodiments of the present invention, in step (1), the metal precursor is a salt including one or more of Pd, Ir, Ru, Rh, Au, Fe, Co, Ni, Cu, Ce, Mn, Zn, and Cr. Preferably, the metal precursor is one or more common salts of Pd, Ir, Ru, Rh, Au, Ce, Mn, Zn and Cr.
In some embodiments of the invention, in step (1), the metal component to catalyst total mass ratio is (10 to 70):100, respectively; preferably, in the step (1), the ratio of the metal component to the total mass of the catalyst is (40-70): 100. here, the metal component refers to the metal in the metal precursor and the metal Pt in the support.
In some embodiments of the present invention, in step (1), the mass ratio of the metal component to the carrier is (10-70): (90-30), the ratio of the carrier to the deionized water is (0.5-20): 100.
In some embodiments of the present invention, in the step (1), the grinding linear velocity is 2 to 30m/s, and the dispersion at the linear velocity can maximally disperse the metal without changing the lattice structure of Pt in the carrier and the pore structure of the carrier, thereby further increasing the loading amount of the metal in the alloy catalyst without affecting the activity of the catalyst, and the scale-up production has reproducibility.
In some embodiments of the present invention, in step (1), the mechanical grinding treatment is performed for 0.5h to 24 h.
In some embodiments of the invention, in step (1), the time for rapid freeze-forming is 0.5 to 10 min. Preferably, in the step (1), the time for rapid freezing and forming is 2-10 min. In experiments, the strong interaction between the Pt/C carrier and the introduced metal is found, the introduced metal is not easy to migrate in the freezing process, the introduced metal and the Pt can be fully bonded by prolonging the time, but the introduced metal still migrates when the time exceeds 10min, so that the alloy components in the catalyst are not uniform, and independent metal nucleation occurs, thereby being very important for controlling the rapid freezing forming time. According to the preparation method of the platinum-based alloy catalyst, in the dispersing and quick freezing processes, due to the strong interaction between metal and the quick freezing process, the metal is confined in the Pt/C structure and is uniformly dispersed on the carrier, the phenomena of metal sedimentation and element segregation are effectively solved, the agglomeration of nano crystals in the high-temperature treatment process is avoided, the high dispersing effect is achieved, due to the strong interaction between metal, the introduced metal can easily enter the lattice structure of Pt, the metal is prevented from forming a phase independently, the dissolution concentration of non-noble metal in an acid solution is extremely low, and acid pickling is not needed in the process.
In some embodiments of the present invention, in step (1), the freezing and forming method includes, but is not limited to, one of dropping the mixed slurry into a low-temperature medium, freezing the slurry in the low-temperature medium, and freezing and drying while mixing in a low-temperature medium in a freeze-drying apparatus.
In some embodiments of the present invention, in step (1), the cryogenic medium includes, but is not limited to, liquid nitrogen, liquid argon, or liquid oxygen, and the freeze-drying device includes, but is not limited to, a rotary dynamic freeze-dryer or a shaking dynamic freeze-dryer. In the method, the freeze drying effect is better than that of the method of freezing by dripping into the low-temperature medium by adopting a mode of mixing, freezing and drying in the low-temperature medium in freeze drying equipment such as a rotary dynamic freeze dryer, a vibration dynamic freeze dryer and the like through actual measurement of the inventor. Therefore, in the step (1), the freeze molding is preferably performed by mixing in a low-temperature medium in a freeze drying apparatus while freezing and drying.
In some embodiments of the present invention, in step (2), the solid mixture obtained in step (1) is transferred or freeze-dried in situ in a vacuum freeze-drying apparatus, wherein the freeze-drying method includes but is not limited to one of bell jar freeze-drying, in situ freeze-drying, rotary dynamic freeze-drying, and shaking dynamic freeze-drying.
In some embodiments of the invention, in step (2), the freeze-drying temperature is 15-80 ℃ and the freeze-drying time is 1-12 h.
In some embodiments of the present invention, in the step (3), the reducing atmosphere is one of hydrogen, CO, a mixed gas containing 1 to 99.5% by volume of hydrogen, and a mixed gas containing 1 to 99.5% by volume of CO. The mixed gas containing 1 to 99.5% by volume of hydrogen and 1 to 99.5% by volume of CO may be an inert gas such as nitrogen or argon, in addition to hydrogen or CO.
In some embodiments of the present invention, in the step (3), the time for rapidly heating the solid powder in the step (2) to the sintering temperature in the reducing atmosphere is 5-20min, the sintering temperature is 300-. Preferably, the sintering time is 1-5 h. It should be noted that, in the step (3), the sintering process adopts rapid temperature rise, and the sintering process adopts rapid temperature reduction, so that the shorter the time, the higher the temperature rise/reduction rate, the metal ions can be reduced in a narrower temperature interval, the dispersibility of crystal grains is better, and meanwhile, the rapid temperature reduction process can generate more stacking faults inside the metal, thereby exposing more active sites and improving the activity of the catalyst.
In order to achieve the above object, a platinum-based alloy catalyst prepared by the above preparation method is provided in the second embodiment of the present invention.
In order to achieve the above object, a third embodiment of the present invention proposes the use of the platinum-based alloy catalyst prepared by the above-described preparation method in a fuel cell. When the catalyst for a fuel cell is used as a cathode and anode catalyst for a fuel cell, the catalyst thickness is typically about 4-15 microns, and to achieve the desired thickness, the catalyst metal to catalyst weight ratio in the cathode catalyst is preferably in the range of (40-70): 100.
The preparation method of the platinum-based alloy catalyst provided by the embodiment of the invention has the beneficial effects that:
(1) from the process perspective: the slurry which is mechanically ground uniformly is quickly frozen, so that the metal is uniformly dispersed on the Pt/C carrier, the phenomena of metal sedimentation and element segregation are effectively solved, the alloy catalyst which is uniformly distributed can be obtained through subsequent drying and quick sintering treatment, and the alloy catalyst has the characteristics of high dispersion and high loading capacity, and is simple in process, few in process steps, high in universality and suitable for large-scale production.
(2) From the innovative point of view: in the mechanical grinding dispersion and quick freezing process, the metal is confined in the Pt/C structure due to the strong interaction between metal and the quick freezing process, so that the metal is uniformly dispersed on a carrier, the phenomena of metal sedimentation and element segregation are effectively solved, the agglomeration of nano-crystals in the high-temperature treatment process is avoided, the high dispersion effect is achieved, the introduced metal is easier to enter the lattice structure of Pt due to the strong interaction between metal, the metal is prevented from forming a phase independently, the inventor verifies that the dissolution concentration of the metal in an acid solution is extremely low, and the subsequent pickling process can be reduced. In the sintering process, the temperature rising/reducing rate is controlled to reduce the catalyst in a narrower temperature region, the metal dispersibility is improved, and stacking faults are generated in the catalyst in the rapid temperature reducing process, so that more active sites are exposed, and the catalyst activity is improved. Due to the high dispersibility of the metal, the loading capacity of the metal can be improved to the maximum extent, the thickness of the catalytic layer of the fuel cell is reduced, the mass transfer efficiency is improved, and further, the metal consumption can be reduced and the catalyst cost is reduced in the application of the fuel cell.
The platinum-based alloy catalyst provided by the embodiment of the invention has the characteristics of high dispersion and high loading capacity, and can be used for fuel cells, so that the consumption of noble metals can be reduced, and the cost of the catalyst can be reduced.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows example 1Pt3ORR LSV curve comparison plot for CO/C, example 3PtNi/C and commercial Pt/C (Cross bar)The coordinate i is the current density, the ordinate E is the potential, RHE is the reversible hydrogen electrode).
FIG. 2 is a graph comparing HOR LSV curves for example 2PtRu/C and commercial Pt/C (current density on the abscissa i, potential on the ordinate E, and reversible hydrogen electrode on the RHE).
FIG. 3 is a TEM image of PtRu/C of example 2.
FIG. 4 is a TEM image of PtPd/C of example 5.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application.
According to the preparation method of the platinum-based alloy catalyst, the Pt/C is used as the carrier, and the metal confinement is enabled to be in the Pt/C structure by means of the strong interaction between metal and metal in the high-energy grinding and quick freezing processes, so that the metal is uniformly dispersed on the carrier, the phenomena of metal sedimentation and element segregation are effectively solved, the agglomeration of nano crystals in the high-temperature treatment process is avoided, the high dispersion effect is achieved, the metal content can reach 40-70%, and the preparation method is incomparable with other existing catalyst preparation methods; meanwhile, due to strong interaction between metals, the introduced metal can easily enter a lattice structure of Pt, so that the metal is prevented from forming a phase independently, and the dissolution concentration of non-noble metal in an acid solution is extremely low and is less than 10 ppm. The platinum-based alloy catalyst prepared by the preparation method of the platinum-based alloy catalyst can reach the commercial standard without acid washing, and the process steps and labor cost can be greatly reduced in industrial production; and the introduced elements are more easily attached to Pt rather than carbon by virtue of the uniformly dispersed Pt particles due to the intermetallic interaction, so that the rapid freeze forming time is not particularly limited, the rapid freeze forming temperature range is wide, and the time is preferably 2-10 min.
According to the preparation method of the platinum-based alloy catalyst, a high-energy grinding mode is selected, so that the dispersing effect is improved, the intermetallic interaction is strengthened, the dispersion degree of the alloy is improved, and the loading capacity is further improved. The increased loading (40-70%) is the goal and high energy milling is the means.
According to the preparation method of the platinum-based alloy catalyst, disclosed by the embodiment of the invention, the rapid heating is adopted to reduce the platinum-based alloy catalyst in a narrow temperature zone, a mode similar to quenching, namely rapid cooling is mainly adopted, and through the process of rapidly cooling to room temperature, more stacking faults can be generated in the material, so that more active sites are exposed, and the activity of the catalyst is improved.
According to the preparation method of the platinum-based alloy catalyst, disclosed by the embodiment of the invention, a high dispersion effect is achieved through intermetallic interaction, the metal dissolution is extremely low, and acid washing is not required.
In the preparation method of the platinum-based alloy catalyst provided by the embodiment of the invention, the limited temperature range of the room temperature is 15-30 ℃.
The raw materials, equipment and the like used in the examples of the present invention are all commercially available products unless otherwise specified.
Example 1
The platinum-based alloy catalyst of this example was Pt3The preparation method of the Co/C comprises the following steps:
(1) weighing 1.0g of 50 wt% Pt/C carrier (C in the Pt/C carrier is carbon black) and 0.202g of cobalt chloride hexahydrate, dispersing in 100mL of deionized water, and treating for 24 hours by adopting a homogenizer (linear velocity 2m/s) to uniformly mix to obtain black slurry;
(2) dropwise adding the black slurry obtained in the step (1) into liquid nitrogen, and quickly freezing (the temperature of a low-temperature medium liquid nitrogen is-196 ℃, and the freezing time is 2min) to obtain a black slurry frozen solid;
(3) freeze-drying the black slurry frozen solid in the step (2) in a freeze dryer at 35 ℃ for 5 hours to obtain a powder mixture;
(4) placing the powder mixture obtained in the step (3) in an atmosphere furnace at 30% H2Mixed gas/Ar atmosphere (H)230 percent), heating to 300 ℃ for 5min, then preserving heat for 5h, cooling to room temperature for 5min to 25 ℃, and obtaining black powder, namely Pt3Co/C catalyst.
The platinum-based alloy catalyst Pt of the example3Co/C as oneElectrochemical testing of oxygen reduction catalysts was performed at 0.1M HClO4Linear sweep testing (0.055-1.205V vs RHE, 50mV/s) and polarization curve testing (10mV/s,1600rpm) were performed in solution and compared to commercial Pt/C, with the results shown in FIG. 1. As can be seen from FIG. 1, Pt3The oxygen reduction activity of CO/C is superior to that of commercial Pt/C.
Example 2
The platinum-based alloy catalyst of the embodiment is PtRu/C, and the preparation method comprises the following steps:
(1) weighing 5.0g of 20 wt% Pt/C carrier (C in the Pt/C carrier is carbon fiber) and 1.34g of ruthenium chloride trihydrate, dispersing in 150mL of deionized water, and treating for 10 hours by a shear mill (linear velocity of 15m/s) to uniformly mix to obtain black slurry;
(2) dropping the black slurry in the step (1) into liquid oxygen for quick freezing (the temperature of low-temperature medium liquid oxygen is-183 ℃, and the freezing time is 10min) to obtain black slurry frozen solid;
(3) freeze-drying the frozen black slurry solid obtained in the step (2) in a freeze dryer at 50 ℃ for 3h to obtain a powder mixture;
(4) placing the powder mixture obtained in the step (3) in an atmosphere furnace, and adding 5% CO/N2In the atmosphere of gas mixture (the volume fraction of CO is 5%), heating to 900 ℃ for 20min, then preserving heat for 1h, and then cooling to 23 ℃ for 30min to obtain black powder, namely the PtRu/C catalyst.
The platinum-based alloy catalyst PtRu/C of the present example was electrochemically tested as a hydrogen oxidation catalyst at 0.1M HClO4Linear scan testing (-0.1-0.6V vs RHE, 50mV/s) and polarization curve testing (10mV/s,1600rpm) were performed in solution and compared to commercial Pt/C, with the results shown in FIG. 2. As can be seen from FIG. 2, the PtRu/C activity is comparable to commercial Pt/C.
The result of transmission electron microscope examination using PtRu/C as the platinum-based alloy catalyst of this example is shown in FIG. 3. As can be seen from fig. 3, the PtRu alloy particles are distributed more uniformly.
Example 3
The platinum-based alloy catalyst of the embodiment is PtNi/C, and the preparation method comprises the following steps:
(1) weighing 5.0g of 40 wt% Pt/C carrier (C in the Pt/C carrier is graphene) and 2.98g of nickel nitrate hexahydrate, dispersing in 20mL of deionized water, and performing sand grinding (linear velocity of 30m/s) for 0.5h to uniformly mix the carrier and the carrier to obtain black slurry;
(2) dropwise adding the black slurry obtained in the step (1) into a liquid argon medium, and quickly freezing (the temperature of the low-temperature medium liquid argon is-186 ℃, and the freezing time is 5min) to obtain black slurry beads;
(3) putting the black slurry beads obtained in the step (2) into a freeze dryer to be subjected to freeze-drying treatment at the temperature of 80 ℃ for 2 hours to obtain a powder mixture;
(4) placing the powder mixture obtained in the step (3) in an atmosphere furnace with 10% H2/N2Atmosphere of mixed gas (H)2The volume fraction is 10%), heating to 500 ℃ for 10min, then preserving heat for 3h, cooling to room temperature 27 ℃ for 15min, and obtaining black powder, namely the PtNi/C catalyst.
The platinum-based alloy catalyst PtNi/C of this example was electrochemically tested as an oxygen reduction catalyst at 0.1M HClO4Linear sweep testing (0.055-1.205V vs RHE, 50mV/s) and polarization curve testing (10mV/s,1600rpm) were performed in solution and compared to commercial Pt/C, with the results shown in FIG. 1. As can be seen from FIG. 1, the oxygen reduction activity of PtNi/C is superior to that of commercial Pt/C.
The platinum-based alloy catalyst PtNi/C of the present example and the platinum-based alloy catalyst Pt of example 1 were mixed3The results of comparing Co/C with commercial PtCo/C with respect to the dissolution concentration of non-Pt metals in the Pt-based alloy are shown in Table 1:
TABLE 1 dissolution concentration of non-Pt metals in Pt-based alloys
| Catalyst and process for preparing same | non-Pt metal elution concentration (ppm) |
| Pt3Co/C | 10 |
| PtNi/C | 8 |
| Commercial PtCo/C | 50-80 |
As is clear from Table 1, PtNi/C, the platinum-based alloy catalyst of the present example, and Pt, the platinum-based alloy catalyst of example 13The non-Pt metal elution concentration of Co/C is much lower than that of commercial PtCo/C.
Example 4
The platinum-based alloy catalyst of the present embodiment is PtIr/CNT (CNT is a carbon nanotube), and the preparation method thereof includes the following steps:
(1) weighing 5.0g of 30 wt% Pt/CNT carrier and 3.96g of chloroiridic acid, dispersing in 120mL of deionized water, and treating for 2 hours by using a sand mill (linear speed of 20m/s) to uniformly mix the Pt/CNT carrier and the chloroiridic acid to obtain slurry;
(2) placing the slurry obtained in the step (1) in a rotary dynamic freeze dryer, quickly freezing in a liquid nitrogen medium (the temperature of the low-temperature medium liquid nitrogen is-196 ℃, and the freezing time is 3min), then heating the slurry to 50 ℃ for in-situ freeze-drying treatment, and completing the freeze-drying process after 3h to obtain a powder mixture;
(3) and (3) placing the powder mixture obtained in the step (2) in an atmosphere furnace, heating to 700 ℃ in an atmosphere of 5% CO/Ar mixed gas (the volume fraction of CO is 5%) for 15min, then preserving the heat for 2h, and then cooling to 18 ℃ at room temperature for 20min to obtain black powder, namely the PtIr/CNT catalyst.
Example 5
The platinum-based alloy catalyst of the present example is PtPd/C, and the preparation method thereof comprises the following steps:
(1) weighing 5.0g of 40 wt% Pt/C carrier (C in the Pt/C carrier is carbon black) and 1.82g of palladium chloride, dispersing in 200mL of deionized water, and treating for 30min by using a homogenizer (linear velocity of 20m/s) to uniformly mix to obtain slurry;
(2) adding the slurry obtained in the step (1) into a vibration type dynamic freeze dryer, quickly freezing in a liquid nitrogen medium (the temperature of a low-temperature medium liquid nitrogen is-196 ℃, and the freezing time is 5min), then heating the slurry to 60 ℃ for in-situ freeze drying, and completing the freeze drying process after 3h to obtain a powder mixture;
(3) placing the powder mixture obtained in the step (2) in an atmosphere furnace with 5% H2/N2Atmosphere of mixed gas (H)2The volume fraction is 5%), heating to 900 ℃ for 20min, then preserving the heat for 1h, cooling to room temperature for 30min to 25 ℃, and obtaining black powder, namely the PtPd/C catalyst.
The result of transmission electron microscope examination using PtPd/C as the platinum-based alloy catalyst of this example is shown in FIG. 4. As can be seen from fig. 4, the PtPd alloy particles are distributed more uniformly.
In summary, the preparation method of the platinum-based alloy catalyst according to the embodiment of the present invention achieves a high dispersion effect by a specific energy mechanical grinding manner without damaging the catalyst structure; the metal confinement is in a Pt/C structure under the condition of extremely cold at low temperature, so that the migration and agglomeration of metal are limited, the agglomeration of nano-crystals in the further high-temperature treatment process is avoided, the introduced metal can easily enter the lattice structure of the existing Pt due to strong interaction between metals, and the independent phase formation of the metal is avoided; through a rapid temperature rising/reducing mode, metal ions are reduced in a narrower temperature region, the dispersion effect of crystal grains can be further improved, more stacking faults can be generated, and the catalytic activity is improved; fourthly, due to high dispersity of the metal, the loading capacity of the metal can be improved to the maximum extent.
The method has the characteristics of simplicity, convenient operation, easy industrial production and the like, reduces the working procedures to a certain extent, shortens the process time, and obtains the catalyst material with the activity superior to that of a commercial catalyst. The catalyst provided by the invention has the characteristics of high dispersion and high loading capacity, so that the consumption of noble metals can be reduced and the cost of the catalyst is reduced in the application of fuel cells.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a platinum-based alloy catalyst is characterized by comprising the following steps:
(1) mechanically grinding and mixing a Pt/C carrier, a metal precursor and deionized water according to a certain proportion, and quickly freezing and molding at (-200) - (-100) DEG C to obtain a solid mixture;
(2) transferring or in-situ freeze drying the solid mixture obtained in the step (1) to obtain solid powder;
(3) and (3) carrying out rapid heating sintering treatment on the solid powder in the step (2) in a reducing atmosphere, and then rapidly cooling to room temperature to obtain a final catalyst product.
2. The method for preparing a platinum-based alloy catalyst according to claim 1, wherein in the step (1), the loading amount of Pt in the Pt/C carrier is 5-60 wt%, the particle size of Pt is 2-6nm, and C in the Pt/C carrier is one or more of carbon fiber, carbon nanotube, graphene, highly graphitized carbon and carbon black.
3. The method for preparing a platinum-based alloy catalyst according to claim 1, wherein in the step (1), the metal precursor is a salt comprising one or more of Pd, Ir, Ru, Rh, Au, Fe, Co, Ni, Cu, Ce, Mn, Zn, and Cr, and the ratio of the metal component to the total mass of the catalyst is (10-70): 100, the mass ratio of the metal component to the carrier is (10-70): (90-30), the ratio of the carrier to the deionized water is (0.5-20): 100.
4. The method of preparing a platinum-based alloy catalyst according to claim 1, wherein the linear grinding speed is 2 to 30m/s and the time for performing the mechanical grinding treatment is 0.5 to 24 hours in step (1).
5. The method for preparing a platinum-based alloy catalyst according to any one of claims 1 to 4, wherein in the step (1), the time for the rapid freeze-forming is 0.5 to 10 min; in the step (1), the freeze molding is one of the modes of dropping the mixed slurry into a low-temperature medium, freezing the slurry in the low-temperature medium, and mixing while freezing and drying in a freeze drying device in the low-temperature medium.
6. The method of preparing a platinum-based alloy catalyst according to claim 5, wherein in the step (1), the cryogenic medium is liquid nitrogen, liquid argon or liquid oxygen, and the freeze-drying device is a rotary dynamic freeze-dryer or a shaking dynamic freeze-dryer.
7. The method for preparing a platinum-based alloy catalyst according to claim 1, wherein in the step (2), the solid mixture obtained in the step (1) is transferred or subjected to freeze drying in situ in a vacuum freeze drying device, and the freeze drying mode is one of bell jar type freeze drying machine freeze drying, in situ freeze drying machine freeze drying, rotary dynamic freeze drying machine freeze drying and shaking type dynamic freeze drying machine freeze drying; in the step (2), the freeze drying temperature is 15-80 ℃, and the freeze drying time is 1-12 h.
8. The method for preparing a platinum-based alloy catalyst according to claim 1, wherein in the step (3), the reducing atmosphere is one of hydrogen, CO, a mixed gas containing 1 to 99.5% by volume of hydrogen, and a mixed gas containing 1 to 99.5% by volume of CO; in the step (3), the time for rapidly heating the solid powder in the step (2) to the sintering temperature is 5-20min under the reducing atmosphere, the sintering temperature is 300-.
9. A platinum-based alloy catalyst, characterized by being produced by the production method according to any one of claims 1 to 8.
10. Use of the platinum-based alloy catalyst prepared by the preparation method according to claims 1 to 8 in a fuel cell.
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