CN112008090B - Chain-shaped metal alloy material and preparation method and application thereof - Google Patents
Chain-shaped metal alloy material and preparation method and application thereof Download PDFInfo
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- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- H—ELECTRICITY
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Abstract
The invention discloses a chain-shaped metal alloy material and a preparation method and application thereof. The preparation method of the chain-shaped metal alloy material comprises the following steps: dipping the transition metal oxide nano particles into a mixed solution containing urea and a platinum source, and reacting to form a transition metal oxide/platinum hydroxide compound; and in a reducing atmosphere, carrying out high-temperature annealing treatment on the transition metal oxide/platinum hydroxide composite to obtain the chain-shaped metal alloy material. The invention utilizes the substitution reaction between the amino group of urea and the carboxyl group of oleic acid wrapping transition metal oxide to connect single transition metal oxide nano particles in series to form a chain shape, pt (OH) 4 Deposition on the surface of transition metal oxide nanoparticles by H 2 And annealing in a reducing atmosphere to successfully prepare the chain-shaped metal alloy material, wherein the chain-shaped metal alloy material has excellent oxygen reduction performance.
Description
Technical Field
The invention belongs to the technical field of energy and cleaning, and particularly relates to a chain-shaped metal alloy material and a preparation method and application thereof.
Background
The problems of energy shortage, climate warming and environmental pollution promote the development of green sustainable energy. Fuel cells are devices that convert chemical energy into electrical energy using fuel and oxygen as raw materials. The fuel cell has the characteristics of greenization, high current density, low weight, compact power generation and the like, and is expected to solve the problems of global environmental pollution and energy supply. The kinetics of the Oxygen Reduction Reaction (ORR) are slow, require a high overpotential, and often require the addition of a catalyst to accelerate the reaction, thereby improving the performance of the fuel cell. The ORR catalyst most commonly used in the industry at present is 20wt% Pt/C, in order to achieve the idealThe performance of fuel cells generally requires higher Pt loading (0.4 mg/cm) 2 ). However, pt is available in small quantities on earth and is expensive. Secondly, in the long-term working process of the Pt/C, pt can fall off from the surface of the carbon carrier and is aggregated to form large nano particles, the stability is poor, and the service life is short. This series of problems severely limits mass production applications of fuel cells. The cost of the catalyst is reduced, and the catalyst with high efficiency, stability and low price is developed, thereby having far-reaching significance for promoting the commercialization of the fuel cell. Rational optimization of the intrinsic activity of Pt-containing active sites and maximum utilization of them are critical to the development of highly efficient Pt-based ORR catalysts. The Pt and the transition metal are alloyed, so that the chemical composition, the electronic structure and the atomic arrangement of the surface of the catalyst can be regulated, the activity and the durability of the catalyst can be improved, and the consumption of the noble metal Pt can be reduced. Generally, the Pt-based alloy catalyst can be prepared by decomposing or reducing a precursor, and how to prepare the Pt-based alloy catalyst with high efficiency, stability and high utilization rate is still the bottleneck of development.
Wang et al (Energy)&Environmental science.2016,9, 2623-2632.Fine-grained and fully ordered intermetallic PtFe catalysts with large engineered catalytic activity and purity.) ordered intermetallic PtFe particles with a particle size of 3.6nm were prepared by liquid phase reduction and retained in porous carbon. The specific activity and mass activity of the catalyst were 20wt% as high as 8 to 10 times of Pt/C. Guo et al (Advance materials.2018, 30, e1705515.Stable High-Index faced Pt Skin on Zigzag-Like PtFe Nanowires Enhances Oxygen Reduction catalysis.) report a Pt with stable High Index crystal plane (HIF) and nanoisolated Pt Skin structure 3 Fe zigzag nano-wires show remarkable electrocatalytic effect in fuel cells. Guo et al (Science bulletin.2020, 65, 97-104.Interface modulation of twin PtFe nanoplates bridged 3D architecture for oxygen reduction catalysis.) also synthesized a novel PtFe nano dendrite oxygen reduction electrocatalyst composed of two-dimensional twin crystal nanoplates, and the Pt skin is formed by heat treatment induction, and the catalyst breaks through the upper limit of ORR performance of the dendritic electrocatalyst. In addition, there have been many studies to develop itHe binary or multi-metal alloy catalysts, such as Pt-Ni (science.2019, 366, 850.Engineering Bunch Pt-Ni alloys for effective oxygen production in reactive fuels), pt-Co (adv.Funct.Mater.2019, 29, 1807340.The Quasi-Pt-alloy Catalyst: hollow PtCo @ single-Atom Pt) 1 on Nitrogen-Doped Carbon toward Superior Oxygen Reduction)、Pt-Cu(Angew.Chem.Int.Ed. 10.1002/anie.202002394.Achieve Superior Electrocatalytic Performance by Surface Copper Vacancy Defects during Electrochemical Etching Process)、Pt-Fe-Cu(Nano Energy.2018，54， 280-287.Core/shell Cu/FePtCu nanoparticles with face-centered tetragonal texture：An active and stable low-Pt catalyst for enhanced oxygen reduction.)。
Based on the above documents, a highly efficient and stable Pt-based alloy catalyst can be prepared, the utilization rate of Pt atoms is not high, and the activity and stability are yet to be further improved.
Disclosure of Invention
The invention mainly aims to provide a chain-shaped metal alloy material, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a chain-shaped metal alloy material, which comprises the following steps:
dipping the transition metal oxide nano particles into a mixed solution containing urea and a platinum source, and reacting to form a transition metal oxide/platinum hydroxide compound;
and in a reducing atmosphere, carrying out high-temperature annealing treatment on the transition metal oxide/platinum hydroxide composite to obtain the chain-shaped metal alloy material.
Further, the transition metal contained in the transition metal oxide nanoparticles includes any one or a combination of two or more of iron, cobalt, and nickel.
Further, the transition metal oxide nanoparticles are ferroferric oxide nanoparticles.
Further, carrying out hydrothermal reaction on a uniformly mixed reaction system containing an iron source, oleic acid, hydroxide, ethanol and water to obtain the ferroferric oxide nano-particles, wherein the temperature of the hydrothermal reaction is 120-210 ℃ and the time is 8-12 h.
Correspondingly, the dosage ratio of the iron source, the oleic acid and the hydroxide is 1-2 mmol: 5-10 g: 0-1 g; the iron source comprises ferrous ammonium sulfate hexahydrate; the volume ratio of ethanol to water in the uniform mixing reaction system is 1: 2-5: 1; the preparation method further comprises the following steps: and after the hydrothermal reaction is finished, collecting the solid matter, and cleaning and drying the solid matter.
Preferably, the drying includes any one of atmospheric drying, freeze drying, and vacuum drying.
The embodiment of the invention also provides the chain-shaped metal alloy material prepared by the method, which is in a nano linear structure and has the diameter of 3-4 nm.
The embodiment of the invention also provides application of the chain metal alloy material in the field of oxygen catalysis or fuel cells.
Correspondingly, the embodiment of the invention also provides an oxygen functional electrocatalyst, which comprises the chain metal alloy material.
Correspondingly, the embodiment of the invention also provides an oxygen functional electro-catalytic electrode (oxygen electrode), which comprises the chain metal alloy material or the oxygen functional electro-catalyst.
Correspondingly, the embodiment of the invention also provides a fuel cell, which comprises the oxygen electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) The chain-like metal alloy material provided by the invention has excellent oxygen reduction performance, low preparation cost and simplicity and feasibility.
(2) The invention utilizes the substitution reaction between the amino of urea and the carboxyl of oleic acid wrapping transition metal oxide to connect single transition metal oxide nano-particles in series to form a chain shape, pt (OH) 4 Deposition on the surface of transition metal oxide nanoparticles by H 2 Annealing in reducing atmosphere to successfully prepareThe chain-shaped metal alloy material is prepared, and the chain-shaped metal alloy material has excellent oxygen reduction performance.
(3) The invention can prepare Fe with different grain diameters by changing experimental conditions 3 O 4 Nano-particles, selecting Fe with different sizes 3 O 4 PtFe alloy nanowires with different diameters can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart illustrating the preparation of a chain metal alloy in example 1 of the present application.
FIGS. 2a and 2b are TEM images of a PtFe alloy at 20nm and 5nm, respectively, in example 1 of the present invention.
FIG. 2c is an electron diffraction pattern of a PtFe alloy in example 1 of the present invention.
FIGS. 2d-e are graphs of HAADF-STEM of PtFe combination in example 1 of the present invention.
FIGS. 2f-i are EDS Mapping charts of PtFe complex in example 1 of the present invention.
Fig. 3 is an XRD pattern of the PtFe alloy in example 1 of the present invention.
FIG. 4 is a graph showing the ORR performance of the PtFe alloy in example 1 of the present invention.
FIG. 5 is a graph showing the current holding ratios of the PtFe alloy and the commercial Pt/C alloy according to example 1 of the present invention as a function of time.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The invention mainly utilizes the substitution reaction between the amino of urea and the carboxyl of oleic acid wrapping transition metal oxide to connect single transition metal oxide nano particles in series to form a chain shape, pt (OH) 4 Deposition on the surface of transition metal oxide nanoparticles by H 2 And annealing in a reducing atmosphere to successfully prepare the chain-shaped metal alloy, so that the stability of the chain-shaped metal alloy is ensured, and the atom utilization rate of Pt in the chain-shaped metal alloy is improved.
The technical solution, its implementation and principles, etc. will be further explained as follows.
It is to be noted that the definitions of the terms mentioned in the description of the present invention are known to those skilled in the art. For example, some of the terms are defined as follows:
1. oxygen functional electrocatalyst: a substance that promotes the rate of oxygen reduction or oxygen evolution reactions under electrochemical conditions.
2. Oxygen functional electrocatalytic electrode: an electrode for generating oxygen catalytic reaction comprises a catalyst, a carbon carrier and a porous electrode.
One aspect of the embodiments of the present invention provides a method for preparing a chain-like metal alloy material, including the steps of:
dipping the transition metal oxide nano particles into a mixed solution containing urea and a platinum source, and reacting to form a transition metal oxide/platinum hydroxide compound;
and in a reducing atmosphere, carrying out high-temperature annealing treatment on the transition metal oxide/platinum hydroxide composite to obtain the chain-shaped metal alloy material.
In some preferred embodiments, the transition metal contained in the transition metal oxide nanoparticles may include any one or a combination of two or more of iron, cobalt, nickel, and the like, but is not limited thereto.
In some preferred embodiments, the transition metal oxide nanoparticles have a particle size of 4-16nm.
In some preferred embodiments, the transition metal oxide nanoparticles are ferroferric oxide nanoparticles.
In some preferred embodiments, the method for preparing the chain-like metal alloy material comprises:
carrying out hydrothermal reaction on a uniformly mixed reaction system containing an iron source, oleic acid, hydroxide, ethanol and water to obtain ferroferric oxide nanoparticles, wherein the temperature of the hydrothermal reaction is 120-210 ℃ and the time is 8-12 h.
Wherein the dosage ratio of the iron source, the oleic acid and the hydroxide is 1-2 mmol: 5-10 g: 0-1 g.
Accordingly, the hydroxide comprises sodium hydroxide and/or potassium hydroxide.
Accordingly, the iron source comprises ferrous ammonium sulfate hexahydrate.
Correspondingly, the volume ratio of the ethanol to the water in the uniform mixing reaction system is 1: 2-5: 1.
Correspondingly, the preparation method further comprises the following steps: and after the hydrothermal reaction is finished, collecting the solid matter, and cleaning and drying the solid matter.
In some preferred embodiments, the drying may include any one of atmospheric drying, freeze drying, vacuum drying, and the like, but is not limited thereto.
In some preferred embodiments, the preparation method specifically comprises: ultrasonically dispersing the transition metal oxide nano particles into an aqueous solution containing urea, adding a platinum source aqueous solution, ultrasonically treating for 30-60 min at the ultrasonic power of 300-650W, heating the obtained mixed solution to 60-100 ℃, and reacting for 12-24h to obtain the transition metal oxide/platinum hydroxide compound.
Accordingly, the platinum source may include one or more of sodium chloroplatinate hexahydrate, chloroplatinic acid, potassium chloroplatinate, and the like, but is not limited thereto.
In some preferred embodimentsIn an embodiment, the preparation method specifically comprises: in reducing atmosphere, heating the transition metal oxide/platinum hydroxide compound to 500-800 ℃, carrying out high-temperature annealing treatment for 0-2H, and then carrying out rare H annealing on the obtained product 2 SO 4 Soaking in the solution, washing and drying to obtain the chain-shaped metal alloy material.
In some more specific embodiments, the method of making specifically comprises: in a reducing atmosphere, the Fe 3 O 4 / Pt(OH) 4 Heating the compound to 500-800 ℃, carrying out high-temperature annealing treatment for 0-2H, and then carrying out diluted H treatment on the obtained product 2 SO 4 Soaking in the solution, washing and drying to obtain a chain-shaped metal alloy material; this step is carried out by reacting Pt (OH) 4 Reduction to Pt, fe 3 O 4 The high temperature of reducing into Fe can also promote Pt and Fe to alloy.
Correspondingly, the preparation method comprises the following steps: heating the transition metal oxide/platinum hydroxide composite to 500-800 ℃ at a heating rate of 5-10 ℃/min.
Correspondingly, the reducing atmosphere comprises a mixed atmosphere of hydrogen and inert gas; preferably, the volume percentage of the hydrogen in the reducing atmosphere is 5-10%.
The chain-like metal alloy material provided by the invention has excellent oxygen reduction performance, low preparation cost and simplicity and feasibility; the method is characterized in that single transition metal oxide nanoparticles are connected in series to form a chain shape by utilizing the substitution reaction between the amino group of urea and the carboxyl group of oleic acid wrapping the transition metal oxide, and Pt (OH) 4 Deposition on the surface of transition metal oxide nanoparticles by H 2 Annealing in reducing atmosphere to successfully prepare the chain-shaped metal alloy material.
Another aspect of an embodiment of the present invention provides a chain-like metal alloy material prepared by the foregoing method, which has a nano-linear structure with a diameter of 3 to 4nm.
The chain metal alloy material obtained by the invention can improve the catalytic activity of the Pt-based catalyst by regulating the type of the transition metal and alloying the transition metal Fe and Pt, and further promote the research and application of fuel cells.
Another aspect of an embodiment of the present invention also provides an application of any one of the chain metal alloy materials in the field of oxygen catalysis or fuel cells.
Another aspect of an embodiment of the present invention also provides an oxygen-functional electrocatalyst, comprising the chain metal alloy material described above.
Further, the oxygen functional electrocatalyst comprises an oxygen reduction electrocatalyst or an oxygen reduction and oxygen evolution bi-functional electrocatalyst.
The embodiment of the invention also provides an oxygen functional electro-catalytic electrode (oxygen electrode) which comprises the chain metal alloy material or the oxygen functional electro-catalyst.
Correspondingly, the embodiment of the invention also provides a fuel cell, which comprises the oxygen electrode.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The preparation flow of the chain-like metal alloy provided by the embodiment is shown in fig. 1, and comprises the following steps:
1. preparation of Fe by hydrothermal method 3 O 4 Nano-particles: 2mM ferrous ammonium sulfate hexahydrate is dissolved in 20mL of deionized water, and the solution is slowly added dropwise into a mixed solution containing 10g of oleic acid, 1g of sodium hydroxide and 20mL of ethanol, and stirred for several minutes at room temperature. Transferring the reaction solution into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the reaction solution at 210 ℃ for 8 hours, naturally cooling, and obtaining a target product Fe through black precipitation at the bottom 3 O 4 . The product can be dissolved in a non-polar solvent, and the product is collected by cyclohexane, centrifuged, and then supernatant fluid is taken and precipitated by ethanol. Washing the obtained precipitate with ethanol for 2-3 times, and drying at 80 ℃ to obtain Fe 3 O 4 And (3) nanoparticles.
2. Preparation of Fe by impregnation 3 O 4 /Pt(OH) 4 The compound is as follows: taking 1.0gFe 3 O 4 Ultrasonic dispersion of nanoparticles200 mu.L of 0.1g/mL aqueous solution of sodium chloroplatinate hexahydrate is added into deionized water containing 300mg of urea, and the mixed solution is heated to 100 ℃ overnight after being subjected to water bath ultrasound for 60 min. And centrifuging, collecting the precipitate, washing with deionized water for three times, and drying for later use.
3. Preparing the PtFe alloy by adopting a high-temperature annealing method: mixing Fe 3 O 4 /Pt(OH) 4 The complex was at 800 ℃ 10% H 2 Annealing for 2h in the Ar atmosphere, wherein the heating rate is 5 ℃/min. The annealed product is in dilute H 2 SO 4 Soaking the PtFe alloy in the solution overnight, then washing the solution to be neutral by deionized water, and drying the solution to obtain the PtFe alloy. As shown in FIGS. 2a and b, the prepared PtFe alloy is in a nanowire structure, and the diameter of the PtFe alloy is about 3-4 nm. By taking the electron diffraction, the (111), (200), (220), (311) and (3) crystal planes of the polycrystalline PtFe in fig. 2c can be observed, which is consistent with the XRD (fig. 3) results. FIG. 2d-e is a diagram of HAADF-STEM of PtFe, first a diagram (2 d) at a lower multiple, which shows an approximate shape of a chain, and second a diagram in which the box is partially enlarged to FIG. 2e; FIGS. 2f-i are EDS Mapping plots of the PtFe alloy of FIG. 2e with the Fe and Pt elements uniformly distributed over the nanowire swept area of the alloy. The PtFe alloy nanowire catalyst shows excellent oxygen reduction catalytic performance, the initial potential is 1.009V, the half-wave potential is 0.886V (figure 4), and the PtFe alloy nanowire catalyst has excellent performance of long circulation, after 25 hours, the current retention rate of the PtFe alloy can reach 83.57%, and the commercial Pt/C is only 48.96% (figure 5).
Example 2
1. Preparation of Fe by hydrothermal method 3 O 4 Nano-particles: 1mM ferrous ammonium sulfate hexahydrate is dissolved in 20mL of deionized water, and the solution is slowly added dropwise into a mixed solution containing 5g of oleic acid, 0g of sodium hydroxide and 20mL of ethanol, and stirred for several minutes at room temperature. Transferring the reaction solution into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the reaction solution at 210 ℃ for 8 hours, naturally cooling, and obtaining a target product Fe through black precipitation at the bottom 3 O 4 . The product can be dissolved in a non-polar solvent, and the product is collected by cyclohexane, centrifuged, and then supernatant fluid is taken and precipitated by ethanol. Washing the obtained precipitate with ethanol for 2-3 times, and drying at 80 ℃ to obtain Fe 3 O 4 And (3) nanoparticles.
2. Preparation of Fe by impregnation 3 O 4 /Pt(OH) 4 The compound is as follows: 0.1g of Fe is taken 3 O 4 Dispersing the nano particles in deionized water containing 30mg of urea by ultrasonic, adding 20 mu L of 0.1g/mL aqueous solution of sodium chloroplatinate hexahydrate, carrying out ultrasonic treatment in a water bath for 30min, and heating the mixed solution to 60 ℃ overnight. And centrifuging, collecting the precipitate, washing with deionized water for three times, and drying for later use.
3. Preparing the PtFe alloy by adopting a high-temperature annealing method: mixing Fe 3 O 4 /Pt(OH) 4 The compound is prepared at 500 deg.C and 5%H 2 Annealing for 1h in the Ar atmosphere, wherein the heating rate is 10 ℃/min. The annealed product is in dilute H 2 SO 4 Soaking the alloy in the solution overnight, then washing the alloy to be neutral by deionized water, and drying the alloy to obtain the PtFe alloy (the morphology is shown in figure 2a and figure 2 b).
Example 3
1. Preparation of Fe by hydrothermal method 3 O 4 Nano-particles: 1.5mM ferrous ammonium sulfate hexahydrate is dissolved in 20mL of deionized water, and the solution is slowly added dropwise to a mixed solution containing 7.5g of oleic acid, 0.5g of sodium hydroxide and 20mL of ethanol, and stirred at room temperature for a few minutes. Transferring the reaction solution into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the reaction solution at 210 ℃ for 8 hours, naturally cooling, and obtaining a target product Fe through black precipitation at the bottom 3 O 4 . The product can be dissolved in a non-polar solvent, and the product is collected by cyclohexane, centrifuged, and then supernatant fluid is taken and precipitated by ethanol. Washing the obtained precipitate with ethanol for 2-3 times, and drying at 80 ℃ to obtain Fe 3 O 4 And (3) nanoparticles.
2. Preparation of Fe by impregnation 3 O 4 /Pt(OH) 4 The compound is as follows: 0.55g of Fe was taken 3 O 4 Dispersing the nano particles in deionized water containing 165mg of urea by ultrasonic wave, adding 110 mu L of 0.1g/mL aqueous solution of sodium chloroplatinate hexahydrate, carrying out ultrasonic treatment in a water bath for 45min, and heating the mixed solution to 80 ℃ overnight. And centrifuging, collecting the precipitate, washing with deionized water for three times, and drying for later use.
3. Preparing the PtFe alloy by adopting a high-temperature annealing method: mixing Fe 3 O 4 /Pt(OH) 4 The compound is at 650 deg.C, 8%H 2 Annealing for 0h in the Ar atmosphere at the temperature rise rate of7 ℃/min. The annealed product is in dilute H 2 SO 4 Soaking the alloy in the solution overnight, then washing the alloy to be neutral by deionized water, and drying the alloy to obtain the PtFe alloy (the morphology is shown in figure 2a and figure 2 b).
Example 4
1. Preparation of Ni by hydrothermal method 3 O 4 Nano-particles: 2mM nickel sulfate hexahydrate was dissolved in 5mL of deionized water, and the solution was slowly added dropwise to a mixed solution containing 10g of oleic acid, 1g of sodium hydroxide and 5mL of ethanol, and stirred at room temperature for several minutes. Transferring the reaction solution into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the reaction solution at the temperature of 120 ℃ for 12 hours, naturally cooling the reaction solution, and obtaining a target product Ni through black precipitation at the bottom 3 O 4 . The product can be dissolved in a non-polar solvent, and the product is collected by cyclohexane, centrifuged, and then supernatant fluid is taken and precipitated by ethanol. Washing the obtained precipitate with ethanol for 2-3 times, and drying at 80 ℃ to obtain Ni 3 O 4 And (3) nanoparticles.
2. Ni preparation by impregnation 3 O 4 /Pt(OH) 4 The compound is as follows: take 0.1 gNi 3 O 4 Dispersing the nano particles in deionized water containing 30mg of urea by ultrasonic, adding 20 mu L of 0.1g/mL aqueous solution of sodium chloroplatinate hexahydrate, carrying out ultrasonic treatment in a water bath for 30min, and heating the mixed solution to 60 ℃ overnight. And centrifuging, collecting the precipitate, washing with deionized water for three times, and drying for later use.
3. Preparing the PtNi alloy by adopting a high-temperature annealing method: mixing Ni 3 O 4 /Pt(OH) 4 The compound is prepared at 500 deg.C and 5%H 2 Annealing for 1h in the Ar atmosphere, wherein the heating rate is 10 ℃/min. The annealed product is in dilute H 2 SO 4 Soaking the PtNi alloy in the solution overnight, then washing the solution to be neutral by using deionized water, and drying the solution to obtain the PtNi alloy.
Example 5
1. Preparation of Co by hydrothermal method 3 O 4 Nano-particles: 2mM cobalt sulfate heptahydrate was dissolved in 12mL of deionized water, and the solution was slowly added dropwise to a mixed solution containing 10g of oleic acid, 1g of sodium hydroxide and 12mL of ethanol, and stirred at room temperature for several minutes. Transferring the reaction solution into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the temperature at 165 ℃ for 10 hours, naturally cooling, and obtaining black bottomPrecipitating as a target product Co 3 O 4 . The product can be dissolved in a non-polar solvent, and the product is collected by cyclohexane, centrifuged, and then supernatant fluid is taken and precipitated by ethanol. Washing the obtained precipitate with ethanol for 2-3 times, and drying at 80 ℃ to obtain Co 3 O 4 And (3) nanoparticles.
2. Preparation of Co by dipping method 3 O 4 /Pt(OH) 4 The compound is as follows: take 0.55gCo 3 O 4 Dispersing the nano particles in deionized water containing 165mg of urea by ultrasonic waves, adding 110 mu L of 0.1g/mL aqueous solution of sodium chloroplatinate hexahydrate, carrying out ultrasonic treatment in a water bath for 45min, and heating the mixed solution to 80 ℃ overnight. And centrifuging, collecting the precipitate, washing with deionized water for three times, and drying for later use.
3. Preparing PtCo alloy by adopting a high-temperature annealing method: mixing Co 3 O 4 /Pt(OH) 4 The compound is at 650 deg.C, 8%H 2 Annealing for 0h in the Ar atmosphere, wherein the heating rate is 7 ℃/min. The annealed product is in dilute H 2 SO 4 Soaking the PtCo alloy in the solution overnight, then washing the solution to be neutral by using deionized water, and drying the solution to obtain the PtCo alloy.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where compositions are described as having, containing, or comprising specific components, or where processes are described as having, containing, or comprising specific process steps, it is contemplated that compositions taught by the present invention also consist essentially of, or consist of, the recited components, and that processes taught by the present invention also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (11)
1. A preparation method of a chain-shaped metal alloy material is characterized by comprising the following steps:
carrying out hydrothermal reaction on a uniformly mixed reaction system containing an iron source, oleic acid, hydroxide, ethanol and water to obtain ferroferric oxide nanoparticles with the particle size of 4-16nm, wherein the dosage ratio of the iron source, the oleic acid and the hydroxide is 1-2 mmol:5 to 10g:0 to 1g, wherein the volume ratio of ethanol to water in the uniformly mixed reaction system is 1:2~5:1, wherein the temperature of the hydrothermal reaction is 120 to 210 ℃, and the time is 8 to 12h;
ultrasonically dispersing the ferroferric oxide nano particles into an aqueous solution containing urea, adding a platinum source, ultrasonically treating for 30-60min at the ultrasonic power of 300-650W, and heating the obtained mixed solution to 60-100 ℃ for reaction for 12-24h to obtain a transition metal oxide/platinum hydroxide compound;
in a reducing atmosphere, heating the transition metal oxide/platinum hydroxide compound to 500-800 ℃, carrying out high-temperature annealing for 0-2H, and then carrying out H-diluted annealing on the obtained product 2 SO 4 Soaking in the solution, washing and drying to obtain the chain-shaped metal alloy material.
2. The method for producing a chain-like metal alloy material according to claim 1, characterized in that: the hydroxide is sodium hydroxide and/or potassium hydroxide; the iron source is ammonium ferrous sulfate hexahydrate.
3. The method for producing a chain-like metal alloy material according to claim 1, further comprising: after the hydrothermal reaction is finished, collecting solid matters, and cleaning and drying the solid matters; wherein the drying is any one of normal pressure drying, freeze drying and vacuum drying.
4. The method for producing a chain-like metal alloy material according to claim 1, characterized in that: the platinum source is one or more of sodium chloroplatinate hexahydrate, chloroplatinic acid or potassium chloroplatinate.
5. The method for producing a chain-like metal alloy material according to claim 1, wherein the production method comprises: heating the transition metal oxide/platinum hydroxide compound to 500-800 ℃ at a heating rate of 5-10 ℃/min.
6. The method for producing a chain-like metal alloy material according to claim 1, characterized in that: the reducing atmosphere is a mixed atmosphere of hydrogen and inert gas, and the volume percentage of the hydrogen in the reducing atmosphere is 5-10%.
7. The chain-like metal alloy material prepared by the method of any one of claims 1 to 6, which has a nano-linear structure and a diameter of 3 to 4nm.
8. Use of the chain metal alloy material according to claim 7 in the field of oxygen catalysis or fuel cells.
9. An oxygen-functional electrocatalyst characterized by comprising the chain metal alloy material according to claim 7; wherein the oxygen function electrocatalyst is an oxygen reduction electrocatalyst or an oxygen reduction and oxygen precipitation bifunctional electrocatalyst.
10. An oxygen electrode comprising the chain metal alloy material according to claim 7 or the oxygen functional electrocatalyst according to claim 9.
11. A fuel cell characterized by comprising the oxygen electrode according to claim 10.
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