CN114784305A - Multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements and preparation method thereof - Google Patents

Multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements and preparation method thereof Download PDF

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CN114784305A
CN114784305A CN202210142315.4A CN202210142315A CN114784305A CN 114784305 A CN114784305 A CN 114784305A CN 202210142315 A CN202210142315 A CN 202210142315A CN 114784305 A CN114784305 A CN 114784305A
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刘韬
高鹏宇
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC 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
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Abstract

The invention provides a multi-component platinum alloy carbon-supported catalyst doped with nonmetallic elements and a preparation method thereof, wherein the preparation method comprises the following steps: the method comprises the following steps of firstly, ultrasonically dispersing a platinum precursor, a transition metal precursor, a surfactant, a non-metal source and a carbon carrier in a specific solvent to obtain a mixture; step two, the mixture is put in an oil bath to reach the oil bath temperature according to the preset heating rate, after the reaction is finished, the mixture is cooled to the room temperature, and then the mixture is centrifugally washed and dried in vacuum to obtain a first catalyst; step three, carrying out acid treatment on the first catalyst by using an acid solution, then carrying out centrifugal washing and vacuum drying to obtain a second catalyst; and step four, annealing the second catalyst at a specific atmosphere and temperature to obtain the non-metallic element doped multi-component platinum alloy carbon supported catalyst. The activity/stability of the catalyst as hydrogen-oxygen fuel cell catalyst is improved by the synergistic and anchoring effect generated by doping the non-metal elements and the multi-component regulation of the transition metal, so that the catalyst is in the leading level in the existing documents and patents, and the one-pot preparation method is suitable for industrial production.

Description

Multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements and preparation method thereof
Technical Field
The invention belongs to the field of catalysts, particularly relates to a catalyst used for a cathode of a proton exchange membrane fuel cell, and particularly relates to a multi-component platinum alloy carbon-supported catalyst doped with a non-metallic element and a preparation method thereof.
Background
The cathode of a Proton Exchange Membrane Fuel Cell (PEMFC) is subjected to an Oxygen Reduction Reaction (ORR), which requires a large overpotential to drive the reaction. Currently, platinum-based catalysts remain the most effective catalysts for cathode ORR, but their expensive cost is one of the important reasons that have hindered PEMFC commercialization. In recent years, a binary platinum-based alloy catalyst becomes an important means for improving the activity and stability of a platinum-based catalyst, but the binary platinum-based alloy prepared by the patent technology still has the problems of high platinum loading capacity, poor activity and stability and the like, so that the problems of reducing the platinum loading capacity of the PEMFC platinum-based catalyst and improving the activity and stability are urgently needed to be solved.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a multi-component platinum alloy carbon-supported catalyst doped with a non-metal element and a method for preparing the same.
The invention provides a preparation method of a multi-component platinum alloy carbon-supported catalyst doped with nonmetallic elements, which is characterized by comprising the following steps: ultrasonically dispersing a platinum precursor, a transition metal precursor, a surfactant, a non-metal source and a carbon carrier in a specific solvent to obtain a mixture; step two, the mixture is put in an oil bath to reach the preset oil bath temperature according to the preset heating rate and is kept for the preset time, after the reaction is finished, the mixture is cooled to the room temperature, centrifugally washed and dried in vacuum at the preset drying temperature, and a first catalyst is obtained; step three, carrying out acid treatment on the first catalyst by using an acid solution under an inert atmosphere, and then carrying out centrifugal washing and vacuum drying again to obtain a second catalyst; and step four, annealing the second catalyst under specific atmosphere, preset annealing temperature and annealing time to obtain the non-metal element doped multi-component platinum alloy carbon-supported catalyst.
The preparation method of the non-metal element doped multi-component platinum alloy carbon supported catalyst provided by the invention also has the following characteristics: wherein the platinum precursor in the first step is one of chloroplatinic acid hexahydrate, sodium chloroplatinate, potassium chloroplatinate and platinum acetylacetonate, the transition metal precursor is at least one of chloride, chlorate, nitrate, acetate and acetylacetone salt of transition metal, the surfactant is at least one of polyvinylpyrrolidone, potassium bromide, hexadecyltrimethylammonium chloride, sodium dodecyl sulfate and benzoic acid, the non-metal source is nitrogen, or at least one of organic salts or inorganic salts containing phosphorus or sulfur, the specific solvent is at least one of oleylamine, oleic acid, 1-octadecene, N-N dimethylformamide, N-N dimethylacetamide, ethylene glycol and triethylene glycol, and the carbon carrier is at least one of carbon black, carbon nanotubes, graphene and acetylene black.
The preparation method of the non-metal element doped multi-component platinum alloy carbon supported catalyst provided by the invention also has the following characteristics: wherein in the first step, the mass ratio of the platinum precursor to the transition metal precursor to the surfactant to the carbon carrier is (10-12):
(125～128)：(100～102)：(40～42)。
the preparation method of the non-metal element doped multi-component platinum alloy carbon-supported catalyst provided by the invention can also have the following characteristics: in the first step, the mass proportion range is 10: 125: 100: 40.
the preparation method of the non-metal element doped multi-component platinum alloy carbon supported catalyst provided by the invention also has the following characteristics: wherein, in the second step, the predetermined heating rate is 1-10 ℃/min, the predetermined oil bath temperature is 100-230 ℃, and the predetermined time is 2-24 h.
The preparation method of the non-metal element doped multi-component platinum alloy carbon-supported catalyst provided by the invention can also have the following characteristics: in the second step, the solvent used for washing the mixture is at least one of deionized water, ethanol, acetone and cyclohexane.
The preparation method of the non-metal element doped multi-component platinum alloy carbon supported catalyst provided by the invention also has the following characteristics: wherein, in the second step, the preset drying temperature is 40-120 ℃.
The preparation method of the non-metal element doped multi-component platinum alloy carbon-supported catalyst provided by the invention can also have the following characteristics: in the third step, the acid solution is at least one of perchloric acid, sulfuric acid, nitric acid and acetic acid, and the molar concentration of the acid solution is 0.1-1 mol/L.
The preparation method of the non-metal element doped multi-component platinum alloy carbon-supported catalyst provided by the invention can also have the following characteristics: wherein, in the fourth step, the annealing temperature is 180-900 ℃, the annealing time is 0.5-10h, and the annealing atmosphere is O2、Ar、NH3And 10% of H2One of the mixed gas of/Ar.
The invention provides a multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements, which is characterized in that: the catalyst is prepared by adopting the preparation method of the multi-component platinum alloy carbon-supported catalyst doped with any one of the nonmetal elements.
The non-metal element doped multi-component platinum alloy carbon supported catalyst provided by the invention also has the following characteristics: wherein the nanometer grain diameter of the multi-component platinum alloy carbon-supported catalyst doped with the non-metallic element is 2-8 nm.
Action and Effect of the invention
The invention provides a multi-component platinum alloy carbon-supported catalyst doped with a non-metallic element and a preparation method thereof, and the nano particles have ideal particle size (about 3.8 nm) and are uniformly dispersed on a carbon carrier. The doping of the non-metallic elements generates the synergistic and anchoring effects and the component regulation of various transition metals, thereby greatly improving the activity and stability of the catalyst. The Rotating Disk Electrode (RDE) test shows that the highest Mass Activity (MA) and the intrinsic activity (SA) of the catalyst (0.9V vs. RHE) can respectively reach 4.79A/mgPtAnd 6.23mA/cm2The mass activity loss after 30000 cycles of potential cycling is 10%, and the activity and the stability of the compound can reach advanced levels in the reported literature and patents at present. At a dose of 0.03mgPt cm-2Loading of the present catalyst was applied to H2in-Air fuel cell cathodes (0.05 mg anode)Pt cm-2) The peak power density can reach 480mW cm-2. Meanwhile, the invention can expand to most transition metals of 4, 5 and 6 periods, and the preparation method of the one-pot method is suitable for industrial production.
Drawings
FIG. 1 is a TEM image of a non-metallic element doped multi-component platinum alloy nanoparticle carbon supported catalyst and the acid treated annealed catalyst in a first example of the present invention; wherein, FIGS. 1(a), (b) and (C) are low-resolution and high-resolution transmission electron microscope images of the PtNiCoCuFe/C-N catalyst synthesized by the one-pot method; FIGS. 1(d), (e) STEM and atom-resolved STEM images of PtNiCoCuFe/C-N catalyst; FIG. 1(f) is an atom-resolved STEM image of the PtNiCoCuFe/C-N catalyst after annealing;
FIG. 2 is a particle size distribution statistical chart of a nitrogen-doped multi-component PtNiCoCuFe/C-N catalyst according to a first embodiment of the present invention;
FIG. 3 is the LSV curve of the other transition metal element synthesis catalyst extended to periods 4, 5 and 6 in the preparation method in the first embodiment of the invention;
FIG. 4 is a LSV curve of a non-metallic element doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C-N in example one of the present invention, a non-N doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C in example two, a binary platinum alloy catalyst PtNi/C in comparative example one, and a commercial Pt/C catalyst in comparative example two;
FIG. 5 is a stability test curve of a non-metallic element doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C-N according to a first embodiment of the present invention;
FIG. 6 is a stability test curve of an N-undoped multicomponent platinum alloy carbon supported catalyst PtNiCoCuFe/C according to a first embodiment of the present invention;
FIG. 7 is a durability test of a commercial Pt/C catalyst in comparative example two of the present invention;
FIG. 8 shows a non-metallic element doped multicomponent platinum alloy carbon supported catalyst PtNiCoCuFe/C-N in H according to a first embodiment of the present invention2Air fuel cell polarization and power density curves.
Detailed Description
The invention provides a multi-component platinum alloy carbon-supported catalyst doped with nonmetallic elements and a preparation method thereof, and the method specifically comprises the following steps:
step one, ultrasonically dispersing a platinum precursor, a transition metal precursor, a surfactant, a non-metal source and a carbon carrier in a specific solvent to obtain a mixture. Wherein the platinum precursor is one of chloroplatinic acid hexahydrate, sodium chloroplatinate, potassium chloroplatinate and platinum acetylacetonate, the transition metal precursor is at least one of chloride, chlorate, nitrate, acetate and acetylacetone salt of transition metal, the surfactant is at least one of polyvinylpyrrolidone, potassium bromide, hexadecyltrimethylammonium chloride, sodium dodecyl sulfate and benzoic acid, the nonmetal source is at least one of nitrogen-containing, phosphorus-containing or sulfur-containing organic salt or inorganic salt, the specific solvent is at least one of oleylamine, oleic acid, 1-octadecene, N-dimethylformamide, N-dimethylacetamide, ethylene glycol and triethylene glycol, the carbon carrier is at least one of carbon black, carbon nano-tube, graphene and acetylene black, the mass ratio of the platinum precursor to the transition metal precursor to the surfactant to the carbon carrier is (10-12): (125-128): (100-102): (40-42), taking 10: 125: 100: 40.
and step two, the mixture is put in an oil bath to reach the preset oil bath temperature according to the preset heating rate and is kept for the preset time, after the reaction is finished, the mixture is cooled to the room temperature, and is centrifugally washed and dried in vacuum at the preset drying temperature, so that the first catalyst is obtained. Wherein the predetermined heating rate is 1-10 ℃/min, the predetermined oil bath temperature is 100-230 ℃, the predetermined time is 2-24h, and the solvent used for washing the mixture is at least one of deionized water, ethanol, acetone and cyclohexane.
And step three, carrying out acid treatment on the first catalyst by using an acid solution under an inert atmosphere, and then carrying out centrifugal washing and vacuum drying again to obtain a second catalyst. The preset drying temperature is 40-120 ℃, the acid solution is at least one of perchloric acid, sulfuric acid, nitric acid and acetic acid, and the molar concentration of the acid solution is 0.1-1 mol/L.
And step four, annealing the second catalyst under specific atmosphere, preset annealing temperature and annealing time to obtain the multi-element high-activity platinum alloy catalyst. The annealing temperature is 180-900 ℃, the annealing time is 0.5-10h, and the annealing atmosphere is O2Ar and 10% of H2Multicomponent complex platinum alloy nano particles in/Ar mixed gasThe diameter is 2-8 nm.
In order to make the technical means, creation features, achievement purposes and effects of the present invention easy to understand, the following embodiments are specifically illustrated with reference to the accompanying drawings.
< example one >
The embodiment provides a multi-component platinum alloy carbon-supported catalyst doped with nonmetallic elements and a preparation method thereof, and the preparation method specifically comprises the following steps:
step one, dispersing 10mg of platinum acetylacetonate, 2.5mg of nickel acetylacetonate, cobalt acetylacetonate, copper acetylacetonate and iron acetylacetonate respectively, 100mg of benzoic acid, 60mg of aminoantipyrine and 40mg of carbon black in 5mL of ethylene glycol by ultrasound to obtain a mixture.
And step two, enabling the mixture to reach the preset oil bath temperature of 160 ℃ in an oil bath according to the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature after the reaction is finished, then carrying out centrifugal washing on the mixture for 3-5 times by using a mixed solution of deionized water, ethanol and acetone, and then carrying out vacuum drying at the preset drying temperature of 60 ℃ overnight to obtain the first catalyst.
Step three, using 0.5M HNO3The first catalyst was subjected to acid treatment under an inert atmosphere at 80 ℃ for 6h, followed by 3 times of centrifugal washing with deionized water and vacuum drying overnight to give a second catalyst.
Step four, the second catalyst is added with 10 percent of H2Annealing at 800 ℃ for 2h in a mixed atmosphere of/Ar, and cooling to obtain the final non-metal element doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C-N.
FIG. 1 is a TEM image of a non-metallic element doped multi-component platinum alloy nanoparticle carbon supported catalyst and the acid treated annealed catalyst in example one of the present inventions; wherein, the images of the PtNiCoCuFe/C-N catalyst synthesized by a one-pot method in the figures 1(a), (b) and (C) are low-resolution and high-resolution transmission electron microscope images; FIGS. 1(d), (e) STEM and atom-resolved STEM images of PtNiCoCuFe/C-N catalyst; FIG. 1(f) is an atom-resolved STEM image of the PtNiCoCuFe/C-N catalyst after annealing. FIG. 2 is a particle size distribution statistical chart of the nitrogen-doped multi-component PtNiCoCuFe/C-N catalyst in the first embodiment of the present invention.
As shown in figures 1 to 2, the multi-component Pt-based alloy nano-particle carbon supported catalyst PtNiCoCuFe/C-N doped with the series non-metallic elements with ideal size (about 3.8 nm) is prepared by a simple and mild one-pot method; the activity and stability of the catalyst are greatly improved through the coordination and anchoring effect of the non-metallic elements and the regulation and control of the multi-component transition metal.
< example two >
The embodiment provides a multi-component platinum alloy catalyst PtNiCoCuFe/C and a preparation method thereof, which is a variation of embodiment 1 and is characterized in that: the non-metal source is removed, and the prepared multi-component platinum alloy catalyst is a PtNiCoCuFe/C catalyst, and the method specifically comprises the following steps:
step one, 10mg of platinum acetylacetonate, 2.5mg of each of nickel acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, and iron acetylacetonate, 100mg of benzoic acid, and 40mg of carbon black were ultrasonically dispersed in 5mL of ethylene glycol to obtain a mixture.
And step two, enabling the mixture to reach the preset oil bath temperature of 160 ℃ in an oil bath according to the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature after the reaction is finished, then carrying out centrifugal washing on the mixture for 3-5 times by using a mixed solution of deionized water, ethanol and acetone, and then carrying out vacuum drying at the preset drying temperature of 60 ℃ overnight to obtain the first catalyst.
Step three, using 0.5M HNO3Carrying out acid treatment on the first catalyst by using the solution in an inert atmosphere, treating for 6h at 80 ℃, then carrying out centrifugal washing for 3 times by using deionized water, and carrying out vacuum drying overnight to obtain a second catalyst;
step four, the second catalyst is added with 10 percent of H2Annealing at 800 ℃ for 2h in a/Ar mixed atmosphere, and cooling to obtain the final N-undoped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C.
< example three >
This embodiment is a modification of embodiment 1, and is modified in that: the transition metal elements of the transition metal precursor in the invention are expanded to most of the transition metal elements of periods 4, 5 and 6, and the rest steps are the same and are not described again.
FIG. 3 is the LSV curve of other transition metal element synthesis catalysts with the preparation method extended to periods 4, 5 and 6 in the first embodiment of the invention.
As shown in fig. 3, the preparation method of the non-metal element doped multi-component platinum alloy carbon supported catalyst provided in this embodiment can be extended to most of transition metal elements in periods 4, 5, and 6, and the one-pot preparation method is suitable for industrial production.
< comparative example one >
In the comparative example, cobalt acetylacetonate, copper acetylacetonate, and iron acetylacetonate in the precursor in the first step of the embodiment are removed to prepare the binary platinum alloy catalyst PtNi/C, which specifically includes the following steps:
step one, 10mg of platinum acetylacetonate, 2.5mg of nickel acetylacetonate, 100mg of benzoic acid and 40mg of carbon black were ultrasonically dispersed in 5mL of N-N dimethylformamide to obtain a mixture.
And step two, enabling the mixture to reach the preset oil bath temperature of 160 ℃ in an oil bath according to the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature after the reaction is finished, then carrying out centrifugal washing on the mixture for 3-5 times by using a mixed solution of deionized water, ethanol and acetone, and then carrying out vacuum drying at the preset drying temperature of 60 ℃ overnight to obtain the first catalyst.
Step three, using 0.5M HNO3Carrying out acid treatment on the first catalyst by using the solution in an inert atmosphere, treating for 6h at 80 ℃, then carrying out centrifugal washing for 3 times by using deionized water, and carrying out vacuum drying overnight to obtain a second catalyst;
step four, the second catalyst is added with 10 percent of H2Annealing at 800 ℃ for 2h in a/Ar mixed atmosphere, and cooling to obtain the final binary platinum alloy catalyst PtNi/C.
Comparative example No. >
In this comparative example, a 60% commercial Pt/C catalyst from Johnson Matthey was used.
Catalyst Performance test experiment
LSV curve
FIG. 4 is a LSV curve of a non-metallic element doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C-N in example one of the present invention, a non-N doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C in example two, a binary platinum alloy catalyst PtNi/C in comparative example one, and a commercial Pt/C catalyst in comparative example two.
As shown in fig. 4, the LSV curve can be calculated as:
the multi-component platinum alloy carbon-supported catalyst PtNiCoCuFe/C-N (at 0.9V vs. RHE) doped with non-metallic elements in the first embodiment has a MA of 4.79A/mgPt and a SA of 6.23mA/cm2(ii) a The N-undoped multicomponent platinum alloy carbon supported catalyst PtNiCoCuFe/C of example two (at 0.9V vs. RHE) had a MA of 3.20A/mgPt and a SA of 4.54 mA/cm2(ii) a The ECSA was calculated to be 70.5m2gPt; the binary platinum alloy catalyst PtNi/C of comparative example I had a Mass Activity (MA) of 1.20A/mgPt and an intrinsic activity (SA) of 1.83 mA/cm2(ii) a The electrochemical surface area (ECSA) was calculated to be 65.7m2gPt; the 60% commercial Pt/C catalyst of comparative example two had a Mass Activity (MA) of 0.1A/mgPt and an intrinsic activity (SA) of 0.18mA/cm2(ii) a The electrochemical surface area (ECSA) was calculated to be 56.1 m2/gPt。
By comparison, the mass activity and intrinsic activity of the multi-component platinum alloy carbon-supported catalyst PtNiCoCuFe/C-N doped with the non-metallic element in the first example are respectively 4 times and 3.4 times of those of the binary platinum alloy catalyst (the first comparative example) and 47.9 times and 34.6 times of those of the commercial Pt/C catalyst (the second comparative example); the MA and SA of the N-undoped multicomponent platinum alloy carbon supported catalyst PtNiCoCuFe/C in example two were 2.7 times and 2.5 times the binary platinum alloy catalyst PtNi/C (comparative example one), and 32 times and 25 times the commercial Pt/C catalyst (comparative example two), respectively. This shows that the activity of the catalysts prepared in examples one and two of the present invention is much higher than that of commercial platinum catalysts on the market, and also has a significant advantage over binary platinum alloys.
The results of the LSV curve-related experiments are summarized in table 1.
TABLE 1 comparison of the properties of the examples with those of the comparative examples
Figure RE-GDA0003685288480000121
2. Stability test
FIG. 5 is a stability test curve of a non-metallic element doped multi-component platinum alloy carbon supported catalyst PtNiCoCuFe/C-N in a first embodiment of the present invention.
As shown in FIG. 5, after 30000 cycles of potential cycling, the MA of the multi-component Pt-Co-Pt-C-N catalyst doped with non-metallic elements in the first example is reduced by 10%, and the stability is at an advanced level in the reported literature and patents.
FIG. 6 is a stability test curve of PtNiCoCuFe/C as an N-undoped multi-component platinum alloy carbon supported catalyst in example two of the present invention.
As shown in FIG. 6, after 30000 cycles of potential cycling, the MA of the N-undoped multicomponent platinum alloy carbon-supported catalyst PtNiCoCuFe/C in example II is reduced by 28%, and the stability thereof is at an advanced level in both the reported literature and the patent.
FIG. 7 is a stability test curve of a commercial Pt/C catalyst according to a comparative example of the present invention.
As shown in fig. 7, the MA decreased 55% after 10000 potential cycles for the commercial Pt/C catalyst.
In addition, the applicant also compared the performance data of the catalyst prepared by the present invention with the performance data of the catalyst described in the top literature in the field, and the comparison results are shown in table 2.
TABLE 2 comparison of catalysts of the invention with the industry top literature
Figure RE-GDA0003685288480000131
Figure RE-GDA0003685288480000141
As shown in Table 2, the activity of the catalyst prepared in example oneThe important performance parameters such as stability, electrochemical specific surface area and the like are superior to most of the currently reported works, and the activity is only lower than that of the individually reported works, such as Pt Jaggd NWs (Science 2016,354,1414), Mo-Pt3Ni (Science 2015,348,1230), but compared with it, the catalyst PtNiCoCuFe/C-N prepared in example one has higher stability (30000 cycles of potential MA reduction by 10%). Importantly, the catalyst PtNiCoCuFe/C-N prepared in example one has the highest half-wave potential (0.97V vs. RHE) compared to the currently reported work, which plays a key role in improving the operating voltage and power density of fuel cells.
FIG. 8 shows a non-metallic element doped multicomponent platinum alloy carbon supported catalyst PtNiCoCuFe/C-N in H according to a first embodiment of the present invention2Air fuel cell polarization and power density curves.
Under the condition of not optimizing the membrane electrode, 0.03mg is usedPt cm-2Ultra low loading of the present catalyst to H2in-Air fuel cell cathodes (0.05 mg anode)Pt cm-2) The peak power density can reach 480mW cm-2。
The conditions specifically adopted in the above embodiments may be further modified as required, and the present invention is not limited by the specific conditions of the above embodiments. It is intended that all such alterations, modifications and variations that fall within the spirit and scope of the invention be embraced by the invention.

Claims (10)

1. A preparation method of a multi-component platinum alloy carbon-supported catalyst doped with a non-metallic element is characterized by comprising the following steps:
ultrasonically dispersing a platinum precursor, a transition metal precursor, a surfactant, a non-metal source and a carbon carrier in a specific solvent to obtain a mixture;
step two, enabling the mixture to reach the preset oil bath temperature in an oil bath according to the preset heating rate and keep the preset time, cooling to room temperature after the reaction is finished, centrifugally washing, and drying in vacuum at the preset drying temperature to obtain a first catalyst;
thirdly, carrying out acid treatment on the first catalyst by using an acid solution under an inert atmosphere, and then carrying out centrifugal washing and vacuum drying again to obtain a second catalyst;
and fourthly, annealing the second catalyst under specific atmosphere, preset annealing temperature and annealing time to obtain the non-metal element doped multi-component platinum alloy carbon-supported catalyst.
2. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
wherein the platinum precursor in the step one is one of chloroplatinic acid hexahydrate, sodium chloroplatinate, potassium chloroplatinate and platinum acetylacetonate,
the transition metal precursor is at least one of chloride, chlorate, nitrate, acetate and acetylacetone salt of transition metal respectively,
the surfactant is at least one of polyvinylpyrrolidone, potassium bromide, hexadecyl trimethyl ammonium chloride, dodecyl sodium sulfate and benzoic acid,
the non-metal source is at least one of organic salt or inorganic salt containing nitrogen, phosphorus or sulfur,
the specific solvent is at least one of oleylamine, oleic acid, 1-octadecene, N-N dimethylformamide, N-N dimethylacetamide, ethylene glycol and triethylene glycol,
the carbon carrier is at least one of carbon black, carbon nano tubes, graphene and acetylene black.
3. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
in the first step, the mass ratio of the platinum precursor to the transition metal precursor to the surfactant to the carbon carrier is (10-12): (125-128): (100-102): (40-42).
4. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 3, wherein the method comprises the following steps:
wherein the mass ratio range is 10: 125: 100: 40.
5. the method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
in the second step, the predetermined heating rate is 1-10 ℃/min, the predetermined oil bath temperature is 100-230 ℃, and the predetermined time is 2-24 h.
6. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
wherein, in the second step, the solvent used for washing the mixture is at least one of deionized water, ethanol, acetone and cyclohexane,
the predetermined drying temperature is 40-120 ℃.
7. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
in the third step, the acid solution is at least one of perchloric acid, sulfuric acid, nitric acid and acetic acid, and the molar concentration of the acid solution is 0.1-1 mol/L.
8. The method for preparing the non-metallic element doped multi-component platinum alloy carbon supported catalyst according to claim 1, wherein the method comprises the following steps:
wherein, in the fourth step, the annealing temperature is 180-900 ℃, the annealing time is 0.5-10h, and the annealing atmosphere is O2、Ar、NH3And 10% of H2One kind of mixed gas of Ar and Ar.
9. A multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements is characterized in that: the preparation method of the multicomponent platinum alloy carbon-supported catalyst doped with the nonmetallic element according to any one of claims 1 to 8.
10. The non-metallic element doped multi-component platinum alloy carbon supported catalyst of claim 9, wherein:
the nano-particle size of the multi-component complex platinum alloy doped with the nonmetallic elements is 2-8 nm.
CN202210142315.4A 2022-02-16 2022-02-16 Multi-component platinum alloy carbon-supported catalyst doped with non-metallic elements and preparation method thereof Pending CN114784305A (en)

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