CN114335580A - Platinum-based alloy catalyst for fuel cell and preparation method thereof - Google Patents
Platinum-based alloy catalyst for fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fuel cell platinum-based alloy catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dispersing transition metal acetylacetone salt and platinum carbon with a molar ratio of 3:1-4:1 in an ethanol solution by utilizing ultrasonic dispersion and magnetic stirring to prepare a pasty mixture; the mixture is dried at constant temperature, annealed, acid-washed and dried to prepare the platinum-based alloy catalyst. Compared with the traditional alloy catalyst synthesis method, the method takes small-size platinum metal nano particles as cores, and successfully diffuses reduced transition metal atoms into the platinum metal particles by utilizing the surface segregation effect of platinum and transition metal and adopting a step-by-step reduction method in the thermal annealing process to form the Pt-M alloy. The preparation method has the characteristics of simple, quick and convenient preparation, and is beneficial to large-scale production and commercial popularization. Meanwhile, the platinum-cobalt alloy catalyst prepared by the invention has high performance and good stability, and is suitable for the oxygen reduction reaction of a fuel cell.
Description
Technical Field
The invention relates to an alloy catalyst and a preparation method thereof, in particular to a fuel cell platinum-based alloy catalyst and a preparation method thereof.
Background
The fuel cell can directly convert chemical energy into electric energy, and has the advantages of high energy utilization rate, environmental protection and zero emission. In a fuel cell, a catalyst is a core component of the fuel cell, and directly affects the energy efficiency and power of the fuel cell. Among many catalysts, Pt-based fuel cell catalysts are the best choice for fuel cell catalysts due to their superior catalytic activity and stability, and are currently the only fuel cell catalysts for commercial applications. However, in the face of the high price and limited earth reserves of Pt, increasing the utilization efficiency of Pt is the technological front of current fuel cells. At present, transition metal elements such as Fe, Co, Ni and the like are alloyed with Pt, so that the use amount of Pt can be reduced, the binding energy of Pt and an oxygen-containing intermediate is weakened, and the catalytic activity is improved.
Among the numerous PtM alloy catalysts, PtCo and PtNi are considered as the two most promising alloy catalysts. Chen et al found that active Pt/t was present in a 0.1 mol/L HCOl4 solution<Pt3Ni/C<Pt3The law of Co/C. The conventional preparation method of the PtM alloy catalyst comprises a microwave-assisted glycol reduction method, a solvothermal reduction method, a hydrogen reduction method and the like. The microwave-assisted reduction method is difficult to synthesize the PtCo alloy catalyst due to the weak reduction capability of ethylene glycol; the solvothermal reduction method uses a large amount of organic solvent and surfactant, and besides pollution caused by the solvothermal reduction method, the addition of the surfactant adsorbs the surfaces of the nano particles, so that the washing difficulty is high, and the organic solvent used in the washing process also causes pollution to the environment.
The Pt-based alloy catalyst prepared by the hydrogen reduction method has strong hydrogen reducibility, and the solid-gas phase reaction is thorough and uniform, so that the method is more favorable for mass production. Patent CN111092235A discloses a platinum-based catalyst for fuel cell and its preparation method, which utilizes freeze-drying method to mix cobalt salt, platinum-carbon catalyst and volatile solvent uniformly, and reduces them in reducing atmosphere. Firstly, the method uses inorganic transition metal salt as a precursor, the required reduction temperature is relatively high, alloy agglomeration is easily caused, and the performance of the catalyst is influenced; meanwhile, the freezing point of the volatile solvent (ethanol and acetone) used in the method is extremely low, the freeze-drying method consumes a large amount of energy and is not in line with the green low-carbon target, and the freeze-drying method has high requirements on equipment and is not beneficial to large-scale commercial production.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a fuel cell platinum-based alloy catalyst which has high and stable catalytic performance and is beneficial to rapid production; another object of the present invention is to provide a method for preparing a platinum-based alloy catalyst for a fuel cell.
The technical scheme is as follows: the fuel cell platinum-based alloy catalyst takes Pt as a shell and transition metal as a core, wherein the molar ratio of the Pt to the transition metal is 2.08-3.12: 1; the transition metal is at least one of Co or Ni; the preparation method of the fuel cell platinum-based alloy catalyst comprises the following steps:
(1) dispersing transition metal acetylacetone salt and platinum carbon in a molar ratio of 3:1-4:1 in an ethanol solution to prepare a pasty mixture;
(2) the mixture is dried at constant temperature, annealed, acid-washed and dried to prepare the platinum-based alloy catalyst.
Further, the fuel cell catalyst is at least one of PtCo, PtNi and PtCoNi; preferably PtCo.
In another aspect, the method for preparing a platinum-based alloy catalyst for a fuel cell of the present invention comprises the steps of:
(1) dispersing transition metal acetylacetone salt and platinum carbon with a molar ratio of 3:1-4:1 in an ethanol solution by utilizing ultrasonic dispersion and magnetic stirring to prepare a pasty mixture; because the catalyst prepared by the method is subjected to the post-treatment method of acid washing, the molar ratio of platinum to transition metal in the actually obtained catalyst sample is not consistent with the feeding ratio, and the final result is the Inductively Coupled Plasma (ICP) test result.
(2) The mixture is dried at constant temperature, annealed, acid-washed and dried to prepare the platinum-based alloy catalyst.
Further, in the step (1), the platinum loading of the platinum carbon is 5-60% by mass, and the platinum loading is preferably 20% by mass.
Further, in the step (1), the volume ratio of the mass of the platinum carbon to the ethanol in the ethanol solution is 2g/L-10 g/L; the preferred ratio of the mass of platinum carbon to the volume of ethanol in the ethanol solution is 8 g/L.
Further, in the step (1), the transition metal in the transition metal acetylacetonate is at least one of Co or Ni.
Further, in the step (2), the annealing temperature is 600-; the preferred annealing temperature is 600 ℃ and the annealing time is 4 h.
Further, in the step (2), the annealing atmosphere is a hydrogen-argon mixed gas or a nitrogen-argon mixed gas.
Further, in the step (2), the reagent used for acid washing is dilute sulfuric acid, the concentration is 0.1-2M, and the acid washing time is 1-24 h.
Compared with the traditional alloy catalyst synthesis method, the method takes small-size platinum metal nano particles as cores, and successfully diffuses reduced transition metal atoms into the platinum metal particles by utilizing the surface segregation effect of platinum and transition metal and adopting a step-by-step reduction method in the thermal annealing process to form the Pt-M alloy. The stepwise reduction method of the invention overcomes the problem of large difference of reduction potential between platinum and transition metal ions, and avoids forming alloy with large grain diameter to influence the activity of the catalyst. Meanwhile, under the conditions of high temperature and hydrogen argon atmosphere, the method is favorable for forming a core-shell structure taking platinum as a shell and transition metal as a core, can improve the overall activity of the catalyst, can reduce the platinum dosage, and has the advantages of economy and high efficiency.
The invention fully utilizes the advantages of organic metal salt of acetylacetone. Firstly, the organic metal salt of acetylacetone is dissolved in ethanol and is slightly soluble in water, and a proper water-alcohol system is selected, so that the solvent can be evaporated at a lower temperature, and the organic metal salt is adsorbed on a platinum-carbon catalyst. Secondly, acetylacetone metal salts are excellent metal complexes whose carbonyl oxygen atoms coordinate with metal ions to form stable six-membered chelate rings. Most of the acetylacetone salt is easy to sublimate, so that the temperature required by reducing metal ions is low, and the grain diameter of the generated alloy is small. Within a certain range, the smaller the particle size of the catalyst of the same type is, the higher the activity of the catalyst is. Therefore, the acetylacetone metal salt has great application prospect in the field of alloy catalyst synthesis.
The invention forms ternary PtM by doping a trace amount of second transition metal1M2Alloy catalyst, change reaction path, and make the catalyst activity higher than original PtM1The alloy performance is improved by 40%. In particular, PtM1M2Is PtCoNi; PtM1For PtCo, trace Ni is doped in PtCo to reduce O2The decomposition barrier makes the reaction easier to be carried out, and the catalyst activity is improved, so that the catalyst activity is improved by 40 percent compared with the performance of the original PtCo alloy.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the catalyst prepared by the method is stable and efficient, is suitable for rapid large-scale production, and is suitable for preparation of different transition metal alloy catalysts compared with the traditional platinum-based catalyst for chemical synthesis;
(2) the method is simple and short in flow, and the well-dispersed platinum-cobalt precursor is prepared only by extremely simple methods such as magnetic stirring dispersion, ultrasonic dispersion and heating evaporation methods; meanwhile, the conventional pH adjustment and addition of a surfactant and a complex are avoided, and the method is efficient, green and environment-friendly.
Drawings
FIG. 1 is a schematic view of a preparation process of the present invention;
FIG. 2 is a graph comparing the ORR of the catalysts prepared in example 1, example 2, example 3 with commercial 20% platinum carbon;
FIG. 3 is a TEM image of the catalyst prepared in example 1;
FIG. 4 is an XRD spectrum of the catalysts prepared in examples 1, 2 and 3;
FIG. 5 is a graph comparing ORRs of example 1 and comparative example 1;
FIG. 6 is a graph comparing ORR of catalysts prepared in comparative examples 2 and 3 and example 1;
FIG. 7 is a comparative ORR chart of the catalysts prepared in comparative examples 4, 5, 6 and examples 1 and 4;
FIG. 8 is a comparative ORR chart of examples 2 and 7 and comparative example 7;
figure 9 is an XRD spectrum of the catalyst prepared in example 7.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
As shown in fig. 1, the PtCo catalyst for a fuel cell is prepared by the following steps:
(1) 64.3mg of cobalt acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added thereto, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature.
(2) And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at the temperature of 600 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. And washing and drying after acid washing to obtain the PtCo catalyst for the fuel cell.
The prepared PtCo catalyst for the fuel cell is subjected to TEM, XRD and ORR tests respectively, wherein the ORR test conditions are as follows: at 25 ℃ in O2And N2ORR polarization curves were recorded at 1600 rpm under 0.1M aqueous perchloric acid saturation.
Example 2
The preparation steps of the PtNi catalyst of the fuel cell are as follows:
(1) 64mg of nickel acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added, and ultrasonic dispersion was carried out for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature.
(2) And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixtureAnd then the mixture is transferred into a tube furnace to be annealed for 4 hours at the temperature of 600 ℃, and the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. And washing and drying after acid washing to obtain the PtNi catalyst for the fuel cell.
The obtained PtNi catalyst for fuel cell was subjected to XRD and ORR tests, respectively, under the same conditions as in example 1.
The prepared fuel cell PtNi catalyst was subjected to an ICP test, and it was found that the Pt: ni is 3.12: 1.
Example 3
The preparation steps of the fuel cell PtCoNi catalyst are as follows:
(1) in a 50ml beaker, 32mg of nickel acetylacetonate and 32.15mg of cobalt acetylacetonate were added, 10ml of ethanol and 5ml of deionized water were added, and ultrasonic dispersion was carried out for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature.
(2) And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at the temperature of 600 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. And washing and drying after acid washing to obtain the PtCoNi catalyst for the fuel cell.
The obtained PtNi catalyst for fuel cell was subjected to XRD and ORR tests, respectively, under the same conditions as in example 1.
As can be seen from FIG. 2, the method of the present invention is suitable for preparing Pt-M alloy catalysts from different transition metals, and has the advantages of stable limiting diffusion current, half-wave voltage far higher than 20% of commercial platinum carbon, and good catalytic performance. The preparation method of the catalyst has universality.
As can be seen from FIG. 3, the alloy particles of the catalyst prepared by the step method in example 1 have small particle size, and the average particle size is 2.36 +/-0.69 nm, which is far smaller than the particle size (5-10 nm) of the conventional platinum-cobalt alloy catalyst. The small particle size is one of the reasons for the high activity of the catalyst.
As can be seen in fig. 4, the diffraction peaks of the three alloy catalysts are all shifted toward high angles relative to the pure Pt diffraction peak, demonstrating the presence of the alloy phase of Pt and transition metal. Especially in the PtCo alloy catalyst, the diffraction peak at 40.5 degrees corresponds to Pt3Co (111) plane, diffraction peak at 47.1 ℃ corresponding to Pt3Co (200) plane, diffraction peak at 68.8 ℃ corresponding to Pt3Co (220) plane, diffraction peak at 83.0 ℃ corresponding to Pt3The (311) crystal plane of Co. Abundant Pt3The existence of Co high-index crystal faces is one of the reasons for high catalyst activity.
Example 4
Compared with the embodiment 1, the difference is that the annealing temperature is 700 ℃, and the specific steps are as follows:
(1) 64.3mg of cobalt acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added thereto, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature.
(2) And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 2 hours at 700 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
Example 5
The differences compared to example 1 are: the molar ratio of cobalt acetylacetonate to platinum carbon is 3: 1; the volume ratio of the mass of the platinum carbon to the ethanol in the ethanol solution is 2g/L, the annealing atmosphere is nitrogen-argon mixed gas, and the annealing time is 1 h; the concentration of dilute sulfuric acid in the acid washing is 0.1M, and the acid washing time is 24 h. The other steps are the same as example 1, and the performance of the finally prepared PtCo catalyst is similar to that of example 1.
Example 6
The differences compared to example 1 are: the molar ratio of cobalt acetylacetonate to platinum carbon is 4: 1; the volume ratio of the mass of the platinum carbon to the ethanol in the ethanol solution is 10g/L, the annealing atmosphere is nitrogen-argon mixed gas, and the annealing time is 6 hours; the concentration of dilute sulfuric acid in the acid washing is 2M, and the acid washing time is 1 h. The other steps are the same as example 1, and the performance of the finally prepared PtCo catalyst is similar to that of example 1.
Example 7
The differences compared to example 3 are: the molar ratio of cobalt acetylacetonate to platinum in the platinum-carbon is 0.1: 1; the molar ratio of nickel acetylacetonate to platinum in the platinum carbon is 3:1, the volume ratio of the mass of the platinum carbon to ethanol in the ethanol solution is 10g/L, the annealing atmosphere is nitrogen-argon mixed gas, and the annealing time is 4 hours; the concentration of dilute sulfuric acid in the acid washing is 2M, and the acid washing time is 1 h. The other steps are the same as example 1, and the PtCoNi alloy catalyst is finally prepared.
The obtained fuel cell PtCoNi catalyst was subjected to XRD, ORR test and ICP test, respectively, wherein the conditions of ORR test were the same as in example 1.
Pt in PtCoNi catalyst was found in ICP test: (Co + Ni) was 2.08: 1.
Comparative example 1
Compared with the embodiment 1, the difference is that the PtCo catalyst is prepared by adopting a one-step method, and the specific steps are as follows:
in a 100ml beaker were added 53.3 mg of chloroplatinic acid hexahydrate, 72.75mg of cobalt nitrate hexahydrate, 78 mg of Vulcan XC-72 carbon powder and 10ml of deionized water. Magnetically stir for 30 minutes. And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 60 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-cobalt precursor. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at 700 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
Fig. 5 shows that the advantage of the step-reduction method is illustrated because the reduced transition metal atoms are successfully diffused into the platinum metal particles by using the surface segregation of platinum and transition metal during the thermal annealing process using small-sized platinum metal nanoparticles as nuclei to form the Pt-M alloy. The stepwise reduction method overcomes the problem of large difference of reduction potential between platinum and transition metal ions, and avoids forming alloy with large grain diameter to influence the activity of the catalyst.
Comparative example 2
Compared with the embodiment 1, the difference is that cobalt sulfate is adopted to replace cobalt acetylacetonate, and the specific steps are as follows:
70.2mg of cobalt sulfate heptahydrate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added, and ultrasonic dispersion was carried out for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature. And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at the temperature of 600 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
Comparative example 3
Compared with the embodiment 1, the difference is that cobalt nitrate is adopted to replace cobalt acetylacetonate, and the specific steps are as follows:
72.75mg of cobalt nitrate hexahydrate, 10ml of ethanol and 5ml of deionized water were added to a 50ml beaker, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature. Transferring the beaker to a constant temperature for heatingHeating the mixture on a table at a constant temperature of 50 ℃ and magnetically stirring the mixture until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at the temperature of 600 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
As can be seen in fig. 6, it is important to illustrate the selection of different metal precursor salts, the advantages of the acetylacetonate salts are as follows:
firstly, the organic metal salt of acetylacetone is dissolved in ethanol and is slightly soluble in water, a proper water-alcohol system is selected, the solvent can be evaporated at a lower temperature, and the organic metal salt is adsorbed on a platinum-carbon catalyst, and the temperature of an impregnation solution is high and is not beneficial to the adsorption of active components because the adsorption is an exothermic reaction; secondly, the acetylacetone metal salt is an excellent metal complex, and the carbonyl oxygen atom of the metal complex is coordinated with metal ions to form a stable hexahydric chelate ring; most of acetylacetone salt is easy to sublimate, so that the temperature required by reducing metal ions is low, and the grain diameter of the generated alloy is small; within a certain range, the smaller the particle size of the catalyst of the same type is, the higher the activity of the catalyst is. Therefore, the acetylacetone metal salt has great application prospect in the field of alloy catalyst synthesis.
Comparative example 4
Compared with the embodiment 1, the difference is that the annealing temperature is 400 ℃, and the specific steps are as follows:
64.3mg of cobalt acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added thereto, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature. And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Mixing the mixtureAfter grinding, the mixture is transferred to a tube furnace to be annealed for 4 hours at the temperature of 400 ℃, and the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
Comparative example 5
Compared with the embodiment 1, the difference is that the annealing temperature is 500 ℃, and the specific steps are as follows:
64.3mg of cobalt acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added thereto, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature. And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring the mixture into a tube furnace to anneal for 4 hours at 500 ℃, wherein the annealing atmosphere is H2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
Comparative example 6
Compared with the embodiment 1, the difference is that the annealing temperature is 800 ℃, and the specific steps are as follows:
64.3mg of cobalt acetylacetonate was added to a 50ml beaker, 10ml of ethanol and 5ml of deionized water were added thereto, and the mixture was ultrasonically dispersed for about 10 minutes. 80mg of 20% Pt @ C platinum carbon catalyst and 5ml of deionized water were added and dispersed by sonication for about 30 minutes. The prepared pasty mixture is magnetically stirred for 3 hours at normal temperature. And transferring the beaker to a constant-temperature heating table, heating at a constant temperature of 50 ℃, and magnetically stirring until the mixture is evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was placed in an air-forced drying oven and dried at 60 ℃ for 8 hours. Grinding the mixture, transferring to a tube furnaceAnnealing at 800 deg.C for 3 hr in H atmosphere2and/Ar, the mass fraction of hydrogen is 5%. The catalyst was washed with 0.05M dilute sulfuric acid for 6 hours at 80 ℃. Washing and drying to obtain the product.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
FIG. 7 shows that the reduction temperature is important for the formation of the alloy and the core-shell structure, and the optimal temperature range is 600-700 ℃.
Comparative example 7
The differences compared to example 1 are: the molar ratio of cobalt acetylacetonate to platinum in the platinum-carbon is 0.1: 1; the volume ratio of the mass of the platinum carbon to the ethanol in the ethanol solution is 10g/L, the annealing atmosphere is nitrogen-argon mixed gas, and the annealing time is 6 hours; the concentration of dilute sulfuric acid in the acid washing is 2M, and the acid washing time is 1 h.
The prepared PtCo catalyst was subjected to ORR test under the same conditions as in example 1.
As can be seen from fig. 8, the alloy catalyst obtained in example 2 and the alloy catalyst obtained in example 7 have the same limiting current density, but in the hybrid region, the half-wave potential of the alloy catalyst obtained in example 7 is significantly higher than that of the alloy catalyst obtained in example 2, indicating that the activity of the ternary alloy catalyst formed by introducing a trace amount of the second transition metal is significantly higher than that of the conventional binary alloy catalyst. The reason is that the two catalysts have different reaction mechanisms, and trace Co element doping changes the reaction path and reduces O2The decomposition barrier makes the reaction easier to proceed and the catalyst activity is improved.
As can be seen from fig. 9, the XRD spectrum of the alloy catalyst prepared in example 7 does not have diffraction peaks of the Pt, Co, and Ni elements alone, which proves that the three elements form a good alloy.
Claims (9)
1. A fuel cell platinum-based alloy catalyst is characterized in that the fuel cell catalyst takes Pt as a shell and takes transition metal as a core, wherein the atomic molar ratio of the Pt to the transition metal is 2.08-3.12: 1; the transition metal is at least one of Co or Ni; the preparation method of the fuel cell platinum-based alloy catalyst comprises the following steps:
(1) dispersing transition metal acetylacetone salt and platinum carbon in a molar ratio of 3:1-4:1 in an ethanol solution to prepare a pasty mixture;
(2) the mixture is dried at constant temperature, annealed, acid-washed and dried to prepare the platinum-based alloy catalyst.
2. The fuel cell platinum-based alloy catalyst according to claim 1, wherein the fuel cell catalyst is at least one of PtCo, PtNi, PtCoNi.
3. A preparation method of a fuel cell platinum-based alloy catalyst is characterized by comprising the following steps:
(1) dispersing transition metal acetylacetone salt and platinum carbon in a molar ratio of 3:1-4:1 in an ethanol solution to prepare a pasty mixture;
(2) the mixture is dried at constant temperature, annealed, acid-washed and dried to prepare the platinum-based alloy catalyst.
4. The method for preparing a platinum-based alloy catalyst for a fuel cell according to claim 3, wherein the platinum carbon in the platinum carbon is loaded in an amount of 5 to 60% by mass in the step (1).
5. The method for preparing a platinum-based alloy catalyst for a fuel cell according to claim 3, wherein in the step (1), the ratio of the mass of the platinum carbon to the volume of the ethanol in the ethanol solution is 2g/L to 10 g/L.
6. The method for preparing a platinum-based alloy catalyst for a fuel cell according to claim 3, wherein in the step (1), the transition metal in the transition metal acetylacetonate is at least one of Co or Ni.
7. The method for preparing the platinum-based alloy catalyst for the fuel cell as recited in claim 3, wherein the annealing temperature in the step (2) is 600-700 ℃, and the annealing time is 1-6 h.
8. The method for producing a platinum-based alloy catalyst for a fuel cell according to claim 3, wherein in the step (2), the annealing atmosphere is a hydrogen-argon mixture gas or a nitrogen-argon mixture gas.
9. The method for preparing a platinum-based alloy catalyst for a fuel cell according to claim 3, wherein in the step (2), the reagent used for acid washing is dilute sulfuric acid with a concentration of 0.1-2M and the acid washing time is 1-24 h.
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