CN118136867A - Double single atom doped carbon coupled Pt3Zn intermetallic compound and preparation method and application thereof - Google Patents

Double single atom doped carbon coupled Pt3Zn intermetallic compound and preparation method and application thereof Download PDF

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CN118136867A
CN118136867A CN202410300086.3A CN202410300086A CN118136867A CN 118136867 A CN118136867 A CN 118136867A CN 202410300086 A CN202410300086 A CN 202410300086A CN 118136867 A CN118136867 A CN 118136867A
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intermetallic compound
diatomic
carbon
doped
salt
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徐强
王启晨
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Southwest University of Science and Technology
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    • YGENERAL 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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Abstract

The invention relates to the technical field of catalyst preparation, in particular to a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent, purifying the obtained mixed solution to obtain MOF precursor powder; performing heat treatment on MOF precursor powder in an inert atmosphere, mixing the obtained diatomic carbon doped with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound. The preparation method can prepare the intermetallic compound catalyst with lower cost and simpler process, has the advantages of high specific surface area, high conductivity, superfine size of intermetallic compound and the like, has a synergistic effect, greatly improves the activity and stability of the catalyst, and is beneficial to improving the performance of devices.

Description

Double single-atom doped carbon coupling Pt 3 Zn intermetallic compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof.
Background
The proton exchange membrane fuel cell (Proton exchange membrane fuel cell, PEMFC) adopts clean hydrogen as fuel, is a high-efficiency energy conversion technology, and has the advantages of high efficiency, high power density and the like. The oxygen reduction reaction (Oxygen reduction reaction, ORR) efficiency determines the PEMFC output performance, and in order to accelerate the ORR kinetics of the PEMFC, a highly active and stable catalyst needs to be used on the cathode side. Currently, platinum and platinum-based alloy catalysts have proven to have excellent ORR catalytic activity; however, the high price and poor stability of commercial Pt-based catalysts limit the commercial application of PEMFCs. On the premise of not reducing the catalytic activity and stability, the reduction of the use amount of noble metal Pt or partial utilization of non-noble metal materials to replace Pt is the focus of research. Researchers often increase the atomic utilization and intrinsic activity of Pt by reducing the size of the Pt nanostructure, surface strain, alloying, or building specific nanostructures with rich Pt surfaces, thereby achieving the goal of reducing Pt loading. In addition, the carrier of the commercial Pt/C catalyst is carbon black (Vulcan XC-72). The bonding between Pt nanoparticles and carbon black support is weak, resulting in dissolution or particle agglomeration of Pt nanoparticles. Carbon black carriers can undergo carbon corrosion in harsh strong acid environments, poisoning Pt nanoparticles, and thus catalyst deactivation.
The martial university Mu et al report that highly dispersed Mn atom doped carbon as a carrier coupled with ultra-fine Pt nanoparticles, the catalyst shows excellent mass activity, good long-term stability and methanol resistance in acidic media. Furthermore, alloying of Pt with transition metals (M, mainly transition metals Fe, co, ni) can enhance the intrinsic ORR activity of Pt. Huang et al, university of california, los Angeles division designed a graphene-nano-pocket-wrapped PtCo nanocatalyst with good ORR performance at the required ultra-low Pt loading due to the non-contact shell of the graphene nano-pocket. Wu et al, university of chinese science and technology, adopted a special mesoporous carbon limiting strategy to obtain ultra-small size Pt-based intermetallic compounds (Pt 3 Co, ptCo and Pt 3 Ti) that exhibited excellent mass activity and ORR durability. The PtMn nanodendrite catalyst is synthesized by Guo et al at Beijing university using solvothermal method, and strain control caused by Mn shrinkage induces simultaneous increase of ORR activity and stability. However, the yield of the solvothermal synthesized material is relatively low, and the solvothermal synthesis method is not suitable for large-scale application.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound, a preparation method and application thereof, and aims to solve the problems that the intrinsic activity of the existing catalyst is low, the yield of a solvothermal synthesized material is low and the like.
The technical scheme of the invention is as follows:
a preparation method of a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound comprises the following steps:
Mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Purifying the mixed solution to obtain MOF precursor powder;
Performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
Mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
And calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the step of preparing a zinc salt, wherein the zinc salt is one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride and zinc oxide; the transition metal salt is selected from one of ferric salt, cobalt salt, nickel salt and manganese salt.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the step of preparing a double monatomic carbon-doped coupled Pt 3 Zn intermetallic compound, wherein the ferric salt is one or more selected from ferric acetate, ferric nitrate, ferric sulfate, ferric chloride and ferric acetylacetonate; the cobalt salt is one or more selected from cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
The preparation method of the double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound comprises the step of preparing a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound, wherein the organic ligand is selected from one or more of imidazole, 2-methylimidazole, 2-nitroimidazole and benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol and deionized water.
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the steps of (1) the mass ratio of zinc salt to transition metal salt (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the step of (4-5) and (1-2) of the mass ratio of the diatomic carbon-doped to the chloroplatinic acid in the chloroplatinic acid aqueous solution.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the steps of heating at a heating rate of 2 ℃/min-20 ℃/min, heating at 800-1100 ℃ and heating for 0.5-10 h.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the steps of heating up at a speed of 2 ℃/min-20 ℃/min, calcining at a temperature of 700 ℃ -1100 ℃ and calcining for 0.5h-3h.
A diatomic carbon-doped coupled Pt 3 Zn intermetallic compound is prepared by a preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound.
The application of double single-atom doped carbon coupling Pt 3 Zn intermetallic compound in proton exchange membrane fuel cell.
The beneficial effects are that: the invention provides a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof, and the preparation method of the double single-atom doped carbon coupling Pt 3 Zn intermetallic compound comprises the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution; purifying the mixed solution to obtain MOF precursor powder; performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon; mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound. According to the invention, the morphology and the size of the MOF are regulated and controlled through the selection of a solvent in the synthesis process, then the MOF precursor powder is subjected to high-temperature pyrolysis, a corresponding Zn-based diatomic carbon-doped carrier material can be derived, and then the superfine Pt 3 Zn intermetallic compound nano particles are anchored on the diatomic carbon-doped through a dipping-reducing atmosphere calcination method, so that the diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound is obtained. The preparation method can prepare the double single-atom doped carbon-coupled superfine Pt 3 Zn intermetallic compound catalyst with lower cost and simpler process, and has the advantages of high specific surface area, high conductivity, superfine size intermetallic compound and the like. In addition, the catalyst has a synergistic effect, greatly improves the activity and stability of the catalyst, and is more beneficial to improving the performance of devices.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a diatomic carbon-doped coupled Pt 3 Zn intermetallic compound according to the present invention;
FIG. 2 is an XRD pattern of an N-doped carbon anchored Fe/Zn diatomic species prepared in example 1;
FIG. 3 is a TEM image of an N-doped carbon-anchored Fe/Zn diatomic group prepared in example 1;
FIG. 4 is an XRD pattern of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 5 is a TEM image of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 6 is a graph showing the particle size distribution of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 7 is an ORR polarization curve of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound prepared in example 5.
Detailed Description
The invention provides a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The Metal-organic framework (Metal-organic framework, MOF) becomes an ideal material conversion platform for constructing single/double-atom doped carbon by virtue of the diversity of Metal ions and functional organic ligands (containing N, P, S and other elements) and the diversity of topological structures and sizes. The MOF is used as a reaction template or a precursor derived carbon-based material, and has the advantages of high specific surface area, porous morphology, adjustment and high dispersion of doped metal elements, controllable graphitization degree, high stability and the like. After pyrolysis, the active metal species supported on the MOF framework are converted to monoatomic sites, which are immobilized on the support by formation of coordination bonds with the coordination atoms (N, S, P, O, etc.) on the carbon support. The construction of the double single-atom doped carbon system is regulated and controlled through reasonable design of the composition, structure and morphology of the MOF precursor.
Based on the above, as shown in fig. 1, the present invention provides a preparation method of a diatomic doped carbon coupled Pt 3 Zn intermetallic compound, comprising the steps of:
step S10: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Step S20: purifying the mixed solution to obtain MOF precursor powder;
Step S30: performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
step S40: mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
Step S50: and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
In the embodiment, the double-single-atom doped carbon prepared by utilizing the pyrolysis of the MOF precursor can improve the bonding effect between the carrier and Pt and improve the stability; meanwhile, double single-atom doped carbon (N-doped carbon anchored double single atoms) can provide a Zn source, and the Zn source is alloyed with Pt nano particles to form the Pt 3 Zn intermetallic compound with high intrinsic activity. The whole preparation process is simple, efficient and environment-friendly, and more importantly, the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound prepared by the preparation method shows excellent ORR performance.
Further, the diatomic carbon-doped coupling intermetallic compound prepared by the preparation method has high specific surface area, high conductivity and ultra-fine size intermetallic compound, and the high specific surface area and the high conductivity are naturally obtained by deriving MOF precursors in the heat treatment process without additional post-treatment; and ultrafine sized intermetallic compounds are formed mainly due to the high specific surface area and the confinement effect of the rich nitrogen coordinating atoms. In addition, the prepared double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound has a synergistic effect, greatly improves the activity and stability of the catalyst, is more beneficial to the improvement of the performance of the device, and simultaneously shows excellent ORR performance.
Specifically, the MOF precursor has excellent structural characteristics of large specific surface area, high porosity and the like, after pyrolysis at high temperature, organic coordination is converted into N-doped carbon, so that the conductivity is improved, metal Zn is evaporated to form a microporous structure, and meanwhile, the structure of the MOF does not collapse, so that the MOF precursor has high specific surface area and a porous structure; after pyrolysis, the active metal species loaded on the MOF framework are converted into monoatomic sites, and the monoatomic sites are fixed on a carrier through coordination bonds formed by coordination atoms (N, S, P, O and the like) on a carbon carrier, so that double monoatoms are formed. Zn in the Zn-rich diatomic doped carbon carrier derived from the MOF precursor diffuses in the calcination process of the reducing atmosphere and combines with Pt to form Pt 3 Zn intermetallic compound.
The PtM intermetallic compound nano particles are prepared independently, and then are loaded on the carbon carrier, so that the metal particles obtained by the method and the carbon carrier mainly depend on physical adsorption, have weak interaction and have low stability. In the double monoatomic doped carbon coupling ultrafine Pt 3 Zn intermetallic compound prepared by the method, a strong coupling effect exists between the Pt 3 Zn intermetallic compound and double monoatomic sites in the carbon carrier, so that interaction between the Pt 3 Zn intermetallic compound and Pt 3 Zn nano particles in the ORR process can be enhanced. Meanwhile, the double monoatomic sites weaken oxygen adsorption on Pt 3 Zn, thereby enhancing intrinsic activity.
In some embodiments, the zinc salt is selected from, but is not limited to, one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc oxide; the transition metal salt is selected from one of iron salt, cobalt salt, nickel salt and manganese salt. And performing heat treatment on MOF precursor powder prepared by mixing zinc salt, transition metal salt, organic ligand and solvent to obtain the Zn-based diatomic doped carbon carrier material.
In some embodiments, in the step S20, the purification treatment includes centrifugation, washing, and drying; the mixed solution is purified to obtain MOF precursor powder with single component.
In some embodiments, in the step S10 and the step S20, the method specifically includes the steps of: dissolving zinc salt and transition metal salt in a solvent to obtain a first mixed solution; dissolving an organic ligand in a solvent to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution, fully stirring for 12 hours at the temperature of 25-80 ℃, standing for 10 hours, centrifuging to realize solid-liquid separation, repeatedly washing with a solvent, and drying to obtain powder which is MOF precursor powder.
In some embodiments, the iron salt is selected from, but not limited to, one or more of iron acetate, iron nitrate, iron sulfate, iron chloride, iron acetylacetonate; the cobalt salt is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
Specifically, when the transition metal is ferric salt, preparing Fe-ZIF-8 precursor; when the transition metal is cobalt salt, a Co-ZIF-8 (ZIF-67) precursor is prepared; when the transition metal is nickel salt, preparing a Ni-ZIF-8 precursor; when the transition metal is manganese salt, mn-ZIF-8 precursor is prepared.
In some embodiments, the zeolitic imidazolate framework-8 (ZIF-8) employed may also be replaced with other MOF precursors, such as MOF-5, MOF-74, uiO-66-NH 2, and the like
In some embodiments, the organic ligand is selected from, but not limited to, one or more of imidazole, 2-methylimidazole, 2-nitroimidazole, benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol, deionized water, but not limited to. The imidazole organic ligand contains N, MOF precursor powder obtained by mixing the imidazole organic ligand with zinc salt and transition metal salt is subjected to heat treatment, and then the ligand is decomposed and converted into N-doped carbon; after pyrolysis, the diatomic atom coordinates with N, and can exist stably. And the type of the solvent can regulate the morphology and the size of the MOF.
In some embodiments, the mass ratio of the zinc salt to the transition metal salt is 1 (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
In some embodiments, the ratio of the mass of the diatomic carbon doped to the mass of chloroplatinic acid in the chloroplatinic acid solution is (4-5): 1-2.
In some embodiments, the step S40 specifically includes the steps of: dispersing the diatomic doped carbon in deionized water to obtain a diatomic doped carbon solution with the concentration of 0.25mg/mL-10 mg/mL; and mixing the diatomic carbon doped solution with chloroplatinic acid solution, and freeze-drying to obtain a mixture.
In some embodiments, the chloroplatinic acid solution is an aqueous solution of chloroplatinic acid; the concentration of the chloroplatinic acid aqueous solution is 1mg/mL-50mg/mL.
In some embodiments, the inert atmosphere includes, but is not limited to, one of nitrogen, argon, a mixture of hydrogen and nitrogen, a mixture of hydrogen and argon.
Specifically, the MOF precursor powder is placed in a porcelain boat, transferred into a tube furnace, introduced with inert atmosphere for 1h, discharged with redundant air in the tube furnace, and then subjected to heat treatment.
In some embodiments, the heat treatment has a heating rate of 2 ℃/min to 20 ℃/min, a temperature of 800 ℃ to 1100 ℃, and a time of 0.5h to 10h. The doping amount of double single atoms, the hierarchical pore structure of the carbon carrier, the graphitization degree and the like can be adjusted by changing the temperature and the time of the heat treatment.
Specifically, the imidazole organic ligand contains N element, pyrolysis is carried out at the temperature of 800-1100 ℃, the ligand is decomposed and converted into N-doped carbon, the higher the temperature is, the more unstable the N is, and the content of N is reduced along with the increase of the pyrolysis temperature; after pyrolysis, the diatomic atoms coordinate with N to exist stably, so the content of N determines the content of the diatomic atoms; the more N indicates a lower degree of graphitization, and the less N indicates a higher degree of graphitization. In the pyrolysis stage, zn volatilizes, the boiling point of Zn is 907 ℃, micropores are generated after Zn volatilizes, and therefore, the hierarchical pore structure can be changed by changing the temperature and time of heat treatment.
In some embodiments, the temperature rise rate of the calcination treatment is 2 ℃/min to 20 ℃/min, the temperature of the calcination treatment is 700 ℃ to 1100 ℃, and the time of the calcination treatment is 0.5h to 3h. The size, crystallinity, order, etc. of Pt 3 Zn can be adjusted by changing the temperature and time of the calcination treatment.
Specifically, the invention adopts dipping-reducing atmosphere calcination, certain mass of diatomic doped carbon is dispersed into deionized water, and a certain amount of chloroplatinic acid aqueous solution is added; the mass part of Pt can be realized by controlling the addition amount of chloroplatinic acid; and then ultrasonic dispersion is carried out to enable Pt ions to be adsorbed on the surface of the double monoatomic doped carbon as soon as possible, then room-temperature stirring is carried out, after freeze drying treatment, the dried precursor powder is calcined in inert atmosphere, the heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, and the heat preservation time is set to 1h. And naturally cooling to obtain black powder, namely the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound.
In some embodiments, the reducing atmosphere includes, but is not limited to, one of a different ratio of hydrogen/argon mixture, a different ratio of hydrogen/nitrogen mixture; preferably, the volume ratio of the hydrogen in the mixed gas is 1% -50%.
In addition, the invention also provides a diatomic carbon-doped coupled Pt 3 Zn intermetallic compound, which is prepared by the preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound.
In the embodiment, the MOF is used as a reaction template or a precursor derived carbon-based material, and the preparation method has the advantages of high specific surface area, porous morphology, adjustment and high dispersion of doped metal elements, controllable graphitization degree, high stability and the like. Meanwhile, the MOF-derived Zn-based diatomic can provide a Zn source for the formation of the superfine Pt 3 Zn intermetallic compound, and the Zn source is not required to be additionally introduced; and the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound can produce a synergistic effect, so that the activity and stability of Pt 3 Zn are improved. Namely, the MOF-derived high specific surface area, zn-rich diatomic and superfine Pt 3 Zn intermetallic compound are utilized to generate a synergistic effect, so that the activity and stability of the catalyst are improved. Meanwhile, the preparation method can realize multiplied production, and has the advantages of simple process, adjustable components and excellent performance.
In addition, the invention also provides application of the double single-atom doped carbon coupling Pt 3 Zn intermetallic compound in a proton exchange membrane fuel cell.
In this embodiment, the application of the diatomic carbon doped coupled Pt 3 Zn intermetallic compound in the electrocatalytic reaction of the exchange membrane fuel cell exhibits excellent performance in electrocatalytic ORR.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation of the N-doped carbon-anchored Fe/Zn diatomic structure in this example comprises the following steps:
50mg of iron acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is Fe-ZIF-8 precursor. Placing the Fe-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Fe/Zn diatomic.
Example 2
The preparation of the N-doped carbon-anchored Co/Zn diatomic includes the following steps:
100mg of cobalt acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is the Co-ZIF-8 precursor. Placing a Co-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Co/Zn diatomic.
Example 3
The preparation of the N-doped carbon-anchored Ni/Zn diatomic includes the following steps:
100mg of nickel acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is the Ni-ZIF-8 precursor. Placing the Ni-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Ni/Zn diatomic.
Example 4
The preparation of the N-doped carbon-anchored Mn/Zn diatomic includes the following steps:
100mg of manganese acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is Mn-ZIF-8 precursor. Placing the Mn-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Mn/Zn diatomic.
Example 5
The Fe/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound prepared in the embodiment comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Fe/Zn diatomic doped carbon (N-doped carbon-anchored Fe/Zn diatomic) prepared in example 1 was weighed into 10mL of deionized water, and then 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Fe/Zn diatomic carbon-doped superfine Pt 3 Zn intermetallic compound.
Example 6
The preparation method of the Co/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Co/Zn diatomic doped carbon (N-doped carbon-anchored Co/Zn diatomic) prepared in example 2 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The temperature rising rate is set to 10 ℃/min, the calcination temperature is set to 900 ℃, and the heat preservation time is set to 1h. The black powder is Co/Zn double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound.
Example 7
The preparation method of the Ni/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Ni/Zn diatomic doped carbon (N-doped carbon-anchored Ni/Zn diatomic) prepared in example 3 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Ni/Zn diatomic carbon-doped superfine Pt 3 Zn intermetallic compound.
Example 8
The Mn/Zn diatomic carbon doped coupling superfine Pt 3 Zn intermetallic compound is prepared in the embodiment, and comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Mn/Zn diatomic doped carbon (N-doped carbon-anchored Mn/Zn diatomic) prepared in example 4 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Mn/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound.
Characterization of the N-doped carbon-anchored Fe/Zn diatomic and Fe/Zn diatomic carbon-coupled ultrafine Pt 3 Zn intermetallic compound prepared in example 1 was performed as follows:
The XRD pattern of the N-doped carbon-anchored Fe/Zn diatomic structure obtained in example 1 is shown in FIG. 2, from which it is clear that the N-doped carbon-anchored Fe/Zn diatomic structure obtained in example 1 does not have any diffraction peaks of metal particles and metal compounds, indicating that Fe/Zn is highly dispersed; the TEM image of the N-doped carbon-anchored Fe/Zn diatomic is shown in fig. 3, and no metal particles and metal compounds were observed with the TEM electron microscope, which is typical of diatomic doped carbon.
The XRD pattern of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound prepared in example 5 is shown in figure 4, and diffraction peaks in XRD are matched with characteristic peaks of standard Pt 3 Zn, which indicates that Pt 3 Zn exists in the sample; the TEM image of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in FIG. 5, the nano particles observed by using a TEM electron microscope are Pt 3 Zn, and the particle size is relatively uniform; the particle size distribution diagram of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in figure 6, and the particle size statistics shows that the size of the Pt 3 Zn nano-particles in figure 5 is concentrated between 2.5nm and 4.5 nm; the ORR polarization curve of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in FIG. 7, and the ORR polarization curve shows that the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound has excellent ORR activity.
In summary, the preparation method and application of the double-single-atom doped carbon-coupled Pt 3 Zn intermetallic compound provided by the invention comprise the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution; purifying the mixed solution to obtain MOF precursor powder; performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon; mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound. According to the invention, the morphology and the size of the MOF are regulated and controlled through the selection of a solvent in the synthesis process, then the MOF precursor powder is subjected to high-temperature pyrolysis, a corresponding Zn-based diatomic carbon-doped carrier material can be derived, and then the superfine Pt 3 Zn intermetallic compound nano particles are anchored on the diatomic carbon-doped through a dipping-reducing atmosphere calcination method, so that the diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound is obtained. The preparation method can prepare the double single-atom doped carbon-coupled superfine Pt 3 Zn intermetallic compound catalyst with lower cost and simpler process, and has the advantages of high specific surface area, high conductivity, superfine size intermetallic compound and the like. In addition, the catalyst has a synergistic effect, greatly improves the activity and stability of the catalyst, and is more beneficial to improving the performance of devices.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (10)

1. The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound is characterized by comprising the following steps:
Mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Purifying the mixed solution to obtain MOF precursor powder;
Performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
Mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
And calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
2. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the zinc salt is selected from one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc oxide; the transition metal salt is selected from one of ferric salt, cobalt salt, nickel salt and manganese salt.
3. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 2, wherein the iron salt is one or more selected from the group consisting of iron acetate, iron nitrate, iron sulfate, iron chloride, and iron acetylacetonate; the cobalt salt is one or more selected from cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
4. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the organic ligand is selected from one or more of imidazole, 2-methylimidazole, 2-nitroimidazole, benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol and deionized water.
5. The method for preparing the diatomic carbon doped coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the mass ratio of the zinc salt to the transition metal salt is 1 (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
6. The method for producing a diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the mass ratio of the diatomic doped carbon to chloroplatinic acid in the chloroplatinic acid solution is (4-5): 1-2.
7. The method for preparing the diatomic carbon doped coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the heating rate of the heat treatment is 2 ℃/min-20 ℃/min, the temperature of the heat treatment is 800 ℃ -1100 ℃, and the time of the heat treatment is 0.5h-10h.
8. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the temperature rise rate of the calcination treatment is 2 ℃/min-20 ℃/min, the temperature of the calcination treatment is 700 ℃ -1100 ℃, and the time of the calcination treatment is 0.5h-3h.
9. A diatomic carbon doped coupled Pt 3 Zn intermetallic compound prepared using the method of preparing a diatomic carbon doped coupled Pt 3 Zn intermetallic compound as defined in any one of claims 1 to 8.
10. Use of a diatomic carbon doped coupled Pt 3 Zn intermetallic compound as defined in claim 9 in a proton exchange membrane fuel cell.
CN202410300086.3A 2024-03-15 2024-03-15 Double single atom doped carbon coupled Pt3Zn intermetallic compound and preparation method and application thereof Pending CN118136867A (en)

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