CN111659419A - Preparation method of carbon-supported platinum-based alloy catalyst - Google Patents
Preparation method of carbon-supported platinum-based alloy catalyst Download PDFInfo
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- CN111659419A CN111659419A CN202010570976.8A CN202010570976A CN111659419A CN 111659419 A CN111659419 A CN 111659419A CN 202010570976 A CN202010570976 A CN 202010570976A CN 111659419 A CN111659419 A CN 111659419A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000007710 freezing Methods 0.000 claims description 16
- 230000008014 freezing Effects 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 229910000990 Ni alloy Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 5
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 210000004911 serous fluid Anatomy 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M4/90—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
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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
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Abstract
The invention provides a preparation method of a carbon-loaded platinum-based alloy catalyst, which comprises the steps of adding a carbon carrier into aqueous solutions of a precursor compound containing platinum and a precursor compound containing transition metal; and then the pH value is regulated in ice bath, the mixture is quickly frozen and dried, and is subjected to heat treatment in reducing atmosphere and post-treatment to obtain the product. The catalyst prepared by the method has good alloy state, the catalytic activity is more than three times of that of common platinum-carbon catalyst, and the preparation method of the invention completely does not use surfactant, reduces the use of chemical reagent and is more beneficial to industrial production.
Description
Technical Field
The invention relates to a preparation method of a noble metal catalyst, in particular to a preparation method of a carbon-supported platinum-based alloy catalyst.
Background
At present, the core material in the fuel cell, namely the catalyst, still generally adopts the type of catalyst of carbon-supported noble metal platinum, and along with the demonstration application of the hydrogen energy fuel cell, especially the popularization and application in the field of transportation public appliances, the demand of the fuel cell is increased, and the consumption of the noble metal platinum is increased, so that the technology direction is always to reduce the consumption of the platinum under the condition of not reducing the performance, even improving the performance. The platinum-based alloy formed by carbon-supported noble metal platinum and other non-noble metals is applied more in the current alternative scheme, and the preparation method thereof adopts a liquid phase reduction method more, for example, Chinese patent application 1026106298155 discloses a method for preparing nano platinum-nickel alloy. However, the current platinum-based alloy catalyst cannot form a platinum-based alloy with good catalytic activity due to the limitation of the preparation method, and thus the use of the platinum-based alloy catalyst in a fuel cell cannot be satisfied.
Disclosure of Invention
The present invention aims to provide a preparation method that can form a carbon-supported platinum-based alloy catalyst having good catalytic activity. The invention is realized by the following scheme.
A preparation method of a carbon-supported platinum-based alloy catalyst comprises the following steps in sequence:
adding a carbon carrier into an aqueous solution of a platinum-containing precursor compound and a transition metal-containing precursor compound to obtain uniformly mixed slurry;
(II) placing the mixed slurry prepared in the step I in an ice bath, and cooling the mixed slurry to-2-1 ℃ under the stirring condition;
(III) rapidly adjusting the pH value of the cooled mixed slurry obtained in the step II to 12-14 by using a strong base solution at a first designated time, wherein the first designated time is not more than 5 minutes;
(IV) rapidly freezing the slurry prepared in step III for a second designated time, and then freeze-drying; the second designated time is not more than 2 minutes;
and (V) placing the platinum-based alloy precursor which is prepared by the step IV and is subjected to freeze drying in a reducing atmosphere, and carrying out heat treatment for more than 6 hours at the temperature of 500-800 ℃.
And in order to prepare the alloy catalyst with better quality, carrying out post-treatment of acid washing, suction filtration and vacuum drying on the product obtained in the step IV to obtain the final product.
Within 3 minutes of the first specified time after the mixed slurry is cooled to the vicinity of the freezing point in the step II, the uniformity of the formed alloy is better.
After the pH value is adjusted in the step III, the mixed slurry is placed in a freezing environment within a second designated time, the certain time is particularly limited, the shorter the time is, the better the performance of the alloy catalyst is, and in the experiment, the more favorable the time limit is 1 minute compared with 2 minutes.
In order to ensure the service performance of the catalyst, in the step I, the molar ratio of the precursor compound containing platinum to the precursor compound containing transition metal is (1-4): 1, and the mass ratio of platinum to the added carbon carrier in the precursor compound containing platinum is 40-60%. The precursor compound containing platinum is one of chloroplatinic acid, potassium chloroplatinite, chloroplatinic acid, sodium chloroplatinite, potassium chloroplatinate and sodium chloroplatinate; the precursor compound containing transition metal is one or more of chloride, sulfate or acetate of iron, cobalt, nickel or copper.
And IV, placing the mixed serous fluid in a freezing environment, and preferably adopting a liquid nitrogen freezing mode.
The reducing atmosphere in the step V is hydrogen, a mixed gas of hydrogen and nitrogen, hydrogen inert gas and the like.
Compared with the prior art, the invention has the following advantages:
1. firstly, the method comprises the following steps: compared with the prior art represented by the preparation of the nano platinum-nickel alloy disclosed in the Chinese patent application 1026106298155, in order to obtain the supported alloy catalyst with better catalytic activity performance, strong alkali for adjusting the pH value is added when the mixed slurry is cooled to the temperature near the freezing point, which is fundamentally different from the step (3) in the preparation method disclosed in the Chinese patent application 1026106298155 that the mixed slurry is placed in an ice bath after the pH value is adjusted. The step of the invention adopts the method, so that the fluidity of the slurry is reduced while alkalization hydrolysis is carried out, the uniformity of the slurry can be improved, and finally, a uniform platinum-based alloy catalyst is obtained, and the second step is as follows: in the present invention, the time interval between the time interval during which the mixed slurry is placed in a freezing environment after the pH of the mixed slurry in the third step is reached is particularly limited, and it has been found that the shorter this time, the better the performance of the alloy catalyst, and that the longer the time interval is, the more the mixed slurry is placed, the less the desired alloy catalyst can be obtained. Therefore, the catalyst prepared by the method has good alloy state, and the catalytic activity is more than three times of that of common platinum-carbon catalysis.
2. The preparation method of the invention does not use surfactant at all, reduces the use of chemical reagent and is more beneficial to industrial production.
Drawings
FIG. 1 Transmission electron micrograph of platinum-nickel alloy catalyst of example 1;
FIG. 2 is a transmission electron micrograph of a comparative example 1 platinum-nickel alloy catalyst;
figure 3 XRD comparison of example 1 and comparative example 1 materials.
Detailed Description
Example 1
A preparation method of a carbon-supported platinum-nickel alloy catalyst comprises the following steps in sequence:
adding 268 mg of activated carbon into an aqueous solution containing 200 mg of potassium chloroplatinate and 22 mg of nickel chloride to obtain mixed slurry;
(II) placing the mixed slurry prepared in the step I in an ice bath, and cooling the mixed slurry to 0 ℃ under the stirring condition;
(III) rapidly adjusting the pH value of the cooled mixed slurry in the step II to 12-14 within 2 minutes by using a sodium hydroxide strong alkali solution;
(IV) quickly freezing the mixed slurry of which the pH value is adjusted in the step III in liquid nitrogen within 1 minute, and then carrying out freeze drying in the liquid nitrogen to obtain a precursor of the platinum-nickel alloy;
(V) heating the platinum-nickel alloy precursor hydrogen prepared by the step IV and subjected to freeze drying and the nitrogen in the mixed reducing atmosphere with the volume of 5:95 at the heating rate of 10 ℃/min to 700 ℃ for heat preservation and heat treatment for 6 hours;
and (VI) carrying out post-treatment of acid washing, suction filtration and vacuum drying on the product obtained in the step V to obtain a final product, namely the carbon-supported platinum-nickel alloy catalyst.
Tests show that the alloy catalyst contains 30% of platinum and the atomic ratio of platinum to nickel is 2.8: 1. The transmission scanning electron microscope of the product is shown in figure 1, and the alloy is relatively uniformly loaded on an activated carbon carrier, and the grain diameter is about 4.0 nm.
Electrochemical tests found that the catalyst prepared in example 1 had an electrochemically active area of 58 m2·g-1And (3) Pt. The catalyst prepared in example 1 had an oxygen reduction mass activity of 0.56 A.g at 0.9V (vs. standard hydrogen electrode)-1Pt, 65% higher mass activity than commercial Pt-Co catalyst.
Comparative example 1
To examine the influence of the interval between the freezing of the mixed slurry in step III and the freezing of the mixed slurry with liquid nitrogen, the procedure of example 1 was completely followed except for the interval, and the interval of comparative example 1 was more than 2 minutes. The transmission electron microscopy of the comparative example 1 material is shown in fig. 2, and the XRD contrast of the example 1 and comparative example 1 materials is shown in fig. 3. As can be seen from a comparison of fig. 1 and 2, the material of example 1 supported a small metal particle size of about 4.0 nm on a carbon support and had a uniform distribution, whereas the material of comparative example 1 supported a larger metal particle size of about 6.0 nm on a carbon support and had a poor distribution uniformity. As can be seen in FIG. 3, the reacted Pt of the example 1 material3The peak of the degree of alloying (111) of the Ni alloy was 41 ° (note: this position was perfect Pt)3Ni1Diffraction peak position of the alloy), whereas the position of the (111) peak of comparative example 1 was 40.4 °, a larger deviation from the 41 ° position, indicating a poorer degree of alloying. The electrochemically active area of the catalyst prepared in comparative example 1 was 42 m2·g-1Pt, about 72% of the active area of the material of example 1. The catalyst prepared in comparative example 1 had an oxygen reduction mass activity of 0.25A g at 0.9V (relative to a standard hydrogen electrode)-1Pt, about only 45% of the oxygen reduction mass activity of the material of example 1.
The comparison experiment shows that when the interval time of freezing the mixed slurry liquid nitrogen after the mixed slurry reaches the pH value exceeds a certain limit value, the formed alloy degree is poor, the catalyst is not uniform, and the electrochemical active area and the quality activity of the catalyst are low.
Example 2
A preparation method of a carbon-supported platinum-cobalt alloy catalyst comprises the following steps in sequence:
adding 375 mg of carbon fiber into an aqueous solution containing 300 mg of sodium chloroplatinite and 90 mg of cobalt acetate to obtain a mixed slurry;
(II) placing the mixed slurry prepared in the step I in an ice bath, and cooling the mixed slurry to-2 ℃ under the stirring condition;
(III) rapidly adjusting the pH value of the cooled mixed slurry in the step II to 12-14 within 3 minutes by using a potassium hydroxide strong alkali solution;
(IV) quickly freezing the mixed slurry of which the pH value is adjusted in the step III in liquid nitrogen within 30 seconds, and then freeze-drying in the liquid nitrogen to obtain a precursor of the platinum-cobalt alloy;
(V) heating the platinum-cobalt alloy precursor hydrogen prepared by the step IV and subjected to freeze drying and the nitrogen in the mixed reducing atmosphere with the volume of 5:95 at the heating rate of 10 ℃/min to 550 ℃ for heat preservation and heat treatment for 9 hours;
and (VI) carrying out post-treatment of acid washing, suction filtration and vacuum drying on the product obtained in the step V to obtain a final product, namely the carbon-supported platinum-cobalt alloy catalyst. Tests show that the content of platinum in the alloy catalyst is 40%, and the atomic ratio of platinum to cobalt is 2.4: 1. The transmission electron microscope of the product shows that the alloy is relatively uniformly loaded on the activated carbon carrier, and the grain diameter is about 5.0 nm. The ORR mass activity of the platinum-cobalt alloy is 0.63A/mg Pt through testing and calculation.
Example 3
A preparation method of a carbon-supported platinum-copper alloy catalyst comprises the following steps in sequence:
adding 240 mg of graphene into an aqueous solution containing 400 mg of chloroplatinic acid and 100 mg of copper sulfate to obtain mixed slurry;
(II) placing the mixed slurry prepared in the step I in an ice bath, and cooling the mixed slurry to 1 ℃ under the stirring condition;
(III) rapidly adjusting the pH value of the cooled mixed slurry in the step II to 12-14 within 5 minutes by using a sodium hydroxide strong alkali solution;
(IV) quickly freezing the mixed slurry of which the pH value is adjusted in the step III in liquid nitrogen within 2 minutes, and then freeze-drying in the liquid nitrogen to obtain a precursor of the platinum-copper alloy;
(V) heating the platinum-copper alloy precursor prepared by the step IV and subjected to freeze drying in a hydrogen reducing atmosphere at the heating rate of 10 ℃/min to 700 ℃ for heat preservation and heat treatment for 8 hours;
and (VI) carrying out post-treatment of acid washing, suction filtration and vacuum drying on the product obtained in the step V to obtain a final product, namely the carbon-supported platinum-copper alloy catalyst.
Tests show that the alloy catalyst contains 60% of platinum and the atomic ratio of platinum to copper is 2: 1. The transmission scanning electron microscope of the product shows that the alloy is relatively uniformly loaded on the activated carbon carrier, and the grain diameter is about 5.2 nm. Through test and calculation, the ORR mass activity of the platinum-copper alloy is 0.48A/mg Pt.
Claims (10)
1. A preparation method of a carbon-supported platinum-based alloy catalyst is characterized by comprising the following steps: the method comprises the following steps of sequentially carrying out,
adding a carbon carrier into an aqueous solution of a platinum-containing precursor compound and a transition metal-containing precursor compound to obtain uniformly mixed slurry;
(II) placing the mixed slurry prepared in the step I in an ice bath, and cooling the mixed slurry to-2-1 ℃ under the stirring condition;
(III) rapidly adjusting the pH value of the cooled mixed slurry obtained in the step II to 12-14 by using a strong base solution at a first designated time, wherein the first designated time is not more than 5 minutes;
(IV) rapidly freezing the slurry prepared in step III for a second designated time, and then freeze-drying; the second designated time is not more than 2 minutes;
and (V) placing the platinum-based alloy precursor which is prepared by the step IV and is subjected to freeze drying in a reducing atmosphere, and carrying out heat treatment for more than 6 hours at the temperature of 500-800 ℃.
2. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1, wherein: and (4) carrying out acid washing, suction filtration and vacuum drying on the product obtained in the step V.
3. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: said first specified time in step III is not greater than 3 minutes.
4. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: and the second designated time in the step IV is not more than 1 minute.
5. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 3, characterized by comprising: and the second designated time in the step IV is not more than 1 minute.
6. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: in the step I, the molar ratio of the precursor compound containing platinum to the precursor compound containing transition metal is (1-4): 1.
7. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 6, wherein: in the step I, the mass ratio of platinum to the added carbon carrier in the precursor compound containing platinum is 40-60%.
8. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: and (4) performing quick freezing in the step IV by adopting a liquid nitrogen freezing mode.
9. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: and the reducing atmosphere in the step V is hydrogen, mixed gas of hydrogen and nitrogen or mixed gas of hydrogen and inert gas.
10. The method for producing a carbon-supported platinum-based alloy catalyst according to claim 1 or 2, characterized by: in the step I, the platinum-containing precursor compound is one of chloroplatinic acid, potassium chloroplatinite, chloroplatinic acid, sodium chloroplatinite, potassium chloroplatinite and sodium chloroplatinate; the precursor compound containing transition metal is one or more of chloride, sulfate or acetate of iron, cobalt, nickel or copper.
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