A multi-component ultrafine pt-based nanowire material and a preparation method thereof

Abstract

The application relates to a multi-component superfine Pt-based nanowire material and a preparation method thereof. The multi-component superfine Pt-based nanowire material is formed by etching and post-treatment or being compounded with other elements based on one-dimensional superfine Pt-Se-M nanomaterial, the multi-component superfine Pt-based nanowire material has the same morphology as the one-dimensional superfine Pt-Se-M nanomaterial, and the one-dimensional superfine Pt-Se-M nanomaterial is synthesized by one-pot wet chemical method from Pt precursors, Se precursors, M precursors, a reducing agent and a solvent. The superfine Pt-based nanowire material has the advantages of high specific surface area, a large number of internal defects, more exposed surface Pt sites, effectively regulated Pt electronic structure compared with commercial Pt / C, and can be used as an anode catalyst of a high-activity direct alcohol fuel cell; and the multi-component superfine Pt-based nanowire material can be prepared without specific morphology control ligands.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanowire materials, and particularly relates to a multi-component ultrafine Pt-based nanowire material and a preparation method thereof. BACKGROUND

[0002] With the implementation of the "double carbon" plan, green energy development, transformation and storage are increasingly valued. Fuel cells are considered one of the most advanced power generation technologies due to their high work efficiency, green environmental protection, long service life and other advantages. The promotion of fuel cells requires the support of advanced catalysts. Benefiting from good high-temperature resistance, oxidation resistance and corrosion resistance, as well as moderate intermediate adsorption characteristics, the current Pt-based catalyst is the most mature catalyst for fuel cells. However, the expensive price and limited global reserves of metal Pt limit the popularization and use of fuel cells. Considering the current irreplaceability of Pt-based catalysts, it is meaningful to perform surface regulation on Pt-based catalysts to improve catalytic activity. Currently, the methods for improving the activity of Pt-based catalysts include: (1) size regulation. Catalytic reaction is a surface reaction, and reducing the size of the catalyst is beneficial to increasing the specific surface area, and then improving the utilization rate of Pt; (2) surface defect construction. The high energy of the defect site reduces the energy barrier of the catalytic reaction, and promotes the catalytic activity; (3) construction of Pt-based dual-component composite materials. The combination of Pt and other elements creates an "alloy effect", which regulates the electronic structure of the surface Pt site, optimizes the adsorption of reaction intermediates on the catalyst surface, and is beneficial to the catalytic activity. Such materials are the most widely studied Pt-based catalysts; (4) synthesis of Pt-based multi-component nanomaterials. The introduction of multi-components promotes the increase of material entropy, and the material presents higher surface hardness, which is beneficial to the catalytic stability. The introduction of more components makes the lattice distortion of the material more serious than that of the dual-component material, which is beneficial to the improvement of catalytic activity.

[0003] During the operation of fuel cells, the severe electrochemical process can easily cause the agglomeration of catalysts. Meanwhile, the strong acid or strong alkali environment can also cause the precipitation of non-noble metal elements in the Pt-based composite catalyst, weakening the alloy effect. Both of these are not conducive to the stability of the catalyst. Due to the anisotropy of the structure, one-dimensional (1D) nanomaterials exhibit better resistance to catalytic agglomeration than zero-dimensional (0D) nanoparticles. In addition, one-dimensional materials have excellent electron transport capacity. Furthermore, increasing the number of elements in the material can effectively improve the surface hardness and increase the resistance to element precipitation, thereby maintaining the catalytic activity for a long time. Therefore, constructing a 1D structure of multi-component ultrafine Pt-based nanomaterials is a good choice to improve the catalytic activity and stability of fuel cells. However, according to the traditional technology, the preparation of such materials with a specific morphology requires a large number of surface ligands for morphology control. However, the use of too many ligands is not conducive to the exposure of active sites on the surface, increases the post-processing procedure of the product, and complicates the production process, which is not conducive to the industrialization of the catalyst. It is even more challenging to obtain a multi-component ultrafine Pt-based nanomaterial with a high concentration of defects by relying on traditional technology. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings in the prior art and provide a multi-component ultrafine Pt-based nanowire material and a preparation method thereof, which can realize the preparation of multi-component ultrafine Pt-based nanowire materials without the presence of specific morphology control ligands.

[0005] The present application is realized by the following technical solutions: on the one hand, a preparation method of a multi-component ultrafine Pt-based nanowire material is provided. The multi-component ultrafine Pt-based nanowire material is based on a one-dimensional ultrafine Pt-Se-M nanomaterial, which is subjected to post-processing such as etching or is combined with other elements to form a multi-component ultrafine Pt-based nanowire material. The multi-component ultrafine Pt-based nanowire material has the same morphology as the one-dimensional ultrafine Pt-Se-M nanomaterial.

[0006] The one-dimensional ultrafine Pt-Se-M nanomaterial is synthesized by one-pot wet chemical method from Pt precursor, Se precursor, M precursor, reducing agent and solvent; and the molar ratio between the Pt precursor, Se precursor, M precursor and reducing agent is as follows:

[0007] Pt precursor: Se precursor = 10: (1-4);

[0008] Pt precursor: M precursor = 10: (1-4);

[0009] Pt precursor: reducing agent = 1: (16-30);

[0010] Among them, M in the M precursor is one or more of Cd, Zn, In, Pd and Ni.

[0011] By the technical scheme, the one-dimensional ultrafine Pt-Se-M nanomaterial is prepared based on one-pot wet chemical method, the material is secondarily treated or further compounded with other elements, on the basis of maintaining the nanowire morphology, the Pt-based nanowire component is regulated, and then the catalytic activity is improved by multiple components.

[0012] The post-treatment method includes chemical etching, electrochemical etching, high-temperature element evaporation based on vapor pressure difference, displacement reaction or synthesis reaction of newly added elements and M elements based on reduction potential difference, etc.

[0013] The post-treatment method also includes introducing other element precursors (N) into the Pt-Se-M synthesis formula to prepare a Pt-Se-M-N multi-component ultrafine Pt-based nanomaterial, that is, introducing element N precursors into a mixed solution synthesized based on Pt precursors, Se precursors and M precursors, and placing the mixed solution in a container for ultrasonic dispersion to be uniform, and then performing the same one-pot wet chemical synthesis as the Pt-Se-M one-dimensional ultrafine nanowire.

[0014] Further, the one-dimensional ultrafine Pt-Se-M nanomaterial is synthesized by the following one-pot wet chemical synthesis method, and the specific steps are as follows:

[0015] Step S1: Pt precursor, Se precursor, M precursor and reducing agent are taken according to the above ratio and placed in a solvent to prepare a mixed solution;

[0016] Step S2: The mixed solution obtained in step S1 is placed in a container for ultrasonic dispersion to be uniform, and a dispersion liquid is obtained;

[0017] Step S3: The container containing the dispersion liquid in step S2 is sealed and heated to 200-250 DEG C and kept for more than 3 hours to obtain a colloidal reaction product;

[0018] Step S4: The colloidal reaction product obtained in step S3 is ultrasonically washed and centrifuged based on the mixed liquid formed by ethanol and cyclohexane to obtain the one-dimensional ultrafine Pt-Se-M nanomaterial.

[0019] By the technical scheme, the preparation process of the application does not involve morphology control ligand, and the one-dimensional ultrafine Pt-Se-M nanomaterial can be prepared by simple one-pot wet chemical method, the overall preparation process is easy to operate, controllable and low in cost, and suitable for large-scale industrial production.

[0020] Further, in step S1, the Pt precursor is one or more of platinum acetylacetone, potassium hexachloroplatinate, platinum chloride, potassium hexabromoplatinate, potassium chloroplatinate and platinum bromide.

[0021] Further, in step S1, the Se precursor is one or more of dibenzyl diselenide, selenium dioxide, selenic acid, selenium powder, potassium selenite.

[0022] Further, in step S1, the reducing agent is one or more of ascorbic acid, glucose, borane pinacol complex, benzoic acid, m-trihydroxybenzoic acid, vitamin C.

[0023] Also provided is a multi-component ultrafine Pt-based nanowire material prepared by the above multi-component ultrafine Pt-based nanowire material preparation method.

[0024] Through the above technical solution, the ultrafine nanometer size exposes more surface Pt sites, the material interior is rich in defects contributing to higher energy, and the entropy increase brought by the multi-component, so that the surface Pt electronic structure of the prepared multi-component Pt-based nanowire is effectively regulated compared with pure Pt. In addition, no excessive morphology control ligand is used in the material synthesis, and the material surface is clean. These factors make the prepared multi-component ultrafine Pt-based nanowire material exhibit extremely high activity in fuel cell catalyst applications. At the same time, the overall multi-component ultrafine Pt-based nanowire preparation process is simple and controllable.

[0025] Further, the Pt molar content in the multi-component ultrafine Pt-based nanowire material is (35-70) at.%, and the Se molar content is (12-25) at.%. Through the above technical solution, the phase structure of the multi-component Pt-based nanomaterial is at least one of an alloy phase, an intermetallic compound phase, and an amorphous phase.

[0026] Further, the morphology of the multi-component ultrafine Pt-based nanowire material is a curved worm-like nanowire, and the distribution state is any one of a single dispersion state of nanowires, a branched state formed by nanowire bridging, and a network state formed by nanowire bridging.

[0027] Further, the multi-component ultrafine Pt-based nanowire material has an ultrafine diameter of 0.5-4 nm, and a length / diameter ratio not less than 10 / 1.

[0028] Through the above technical solution, the ultrafine nanowire structure has a significant structural anisotropy effect compared with the ultra-small nanoparticle, which can effectively avoid catalyst agglomeration and growth in harsh electrochemical processes, and prolong the service life of the catalyst.

[0029] Further, the multi-component ultrafine Pt-based nanowire material is rich in a large number of defects inside, at least including one of the following defect types: vacancies, interstitial atoms, lattice distortion, dislocations, and interfaces.

[0030] Through the technical scheme, more surface Pt sites are exposed by the ultrafine nanometer size, defects inside the material contribute higher energy, and entropy increase is caused by multiple elements, so that the surface Pt electronic structure of the prepared multiple element Pt-based nanowire is effectively regulated compared with pure Pt.

[0031] The present application has the advantages of:

[0032] ① The present application solves the problem of easy agglomeration of the catalyst in the field of fuel cell catalysis, which leads to a decrease in stability.

[0033] ② The present application provides a new type of ultrafine Pt-based nanowire material with rich defects and multiple elements, which benefits from the entropy increase effect, defect effect, and nanowire structure effect. More surface Pt sites are exposed by the ultrafine nanometer size, defects inside the material contribute higher energy, and entropy increase is caused by multiple elements, so that the surface Pt electronic structure of the prepared multiple element Pt-based nanowire is effectively regulated compared with pure Pt.

[0034] ③ The ultrafine nanowire structure of the present application has a significant structural anisotropy effect compared with ultra-small nanoparticles, which can effectively avoid catalyst agglomeration and growth in harsh electrochemical processes, prolonging the service life of the catalyst. The catalytic activity and stability of the present application are significantly enhanced compared with commercial Pt / C catalyst, fully solving the problem of easy agglomeration of existing catalysts in operation.

[0035] ④ The present application provides a green synthesis strategy. The synthesis process does not involve morphology control ligands, and Pt-Se-M ultrafine nanowires can be obtained by a simple one-pot wet chemical method. Secondary processing or further compounding with other elements is performed on the ultrafine nanowires, realizing the regulation of Pt-based nanowire components on the basis of maintaining the morphology of the nanowires, and then realizing the improvement of the catalytic activity of multiple elements.

[0036] ⑤ The overall preparation process of the present application is easy to operate, has good controllability, and is low in cost, being suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is the preparation process flow chart of the multiple element ultrafine Pt-based nanowire material of the present application;

[0038] Figure 2 is the high and low magnification TEM graph (a, b) and nanowire diameter statistical analysis (c) of the multiple element ultrafine Pt-based nanowire prepared in Example 1 of the present application;

[0039] Figure 3 is the element EDS mapping distribution graph of the multiple element ultrafine Pt-based nanowire prepared in Example 1 of the present application;

[0040] Figure 4This is the elemental EDS diagram of the multi-component ultrafine Pt-based nanowires prepared in Example 1 of this invention;

[0041] Figure 5 This is the XRD pattern of the multi-component ultrafine Pt-based nanowires prepared in Example 1 of this invention;

[0042] Figure 6 This is a high-resolution TEM image of the multi-component ultrafine Pt-based nanowires prepared in Example 1 of the present invention, wherein the red dashed lines represent grain boundary locations;

[0043] Figure 7 These are TEM images of the Pt-M and Pt-Se nanomaterials obtained after removing the Se and M precursors in the synthesis reaction formulation of Example 1.

[0044] Figure 8 This is a TEM image of the multi-component ultrafine Pt-based nanowires prepared in Example 2 of this invention;

[0045] Figure 9 This is a TEM image of the multi-component ultrafine Pt-based nanowires prepared in Example 3 of this invention;

[0046] Figure 10 This is a TEM image of the multi-component ultrafine Pt-based nanowires prepared in Example 4 of this invention;

[0047] Figure 11 This is a TEM image of the multi-component ultrafine Pt-based nanowires prepared in Example 5 of this invention;

[0048] Figure 12 This is a comparison of the MOR performance of the nanowire catalyst prepared by loading multi-component ultrafine Pt-based nanowires onto a carbon support in Example 1 of this invention and a commercial Pt / C catalyst in a 0.1M HClO4 + 0.5M Methanol solution.

[0049] Figure 13 This is a comparison of the EOR performance of the nanowire catalyst prepared by loading multi-component ultrafine Pt-based nanowires onto a carbon support in Example 2 of this invention and a commercial Pt / C catalyst in a 0.1M HClO4 + 0.5M Ethanol solution. Detailed Implementation

[0050] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or," and the use of the term "comprising" and other forms is non-limiting.

[0051] In one aspect of the present application, a method for preparing a multi-component ultrafine Pt-based nanowire material is provided. The multi-component ultrafine Pt-based nanowire material is obtained by etching or other post-processing of a one-dimensional ultrafine Pt-Se-M nanomaterial or by compounding the one-dimensional ultrafine Pt-Se-M nanomaterial with other elements. The multi-component ultrafine Pt-based nanowire material has the same morphology as the one-dimensional ultrafine Pt-Se-M nanomaterial.

[0052] The one-dimensional ultrafine Pt-Se-M nanomaterial is synthesized by a one-pot wet chemical method using a Pt precursor, a Se precursor, an M precursor, a reducing agent, and a solvent.

[0053] The post-processing method further includes introducing an N precursor into the Pt-Se-M synthesis formula to prepare a Pt-Se-M-N multi-component ultrafine Pt-based nanomaterial. That is, based on the synthesis of the Pt precursor, the Se precursor, and the M precursor, an N precursor is introduced to form a mixed solution, which is then ultrasonically dispersed in a container until uniform. Subsequently, the same wet chemical synthesis operation as for the one-dimensional ultrafine Pt-Se-M nanowire is performed.

[0054] Specifically, a method for preparing a multi-component ultrafine Pt-based nanowire material includes the following steps:

[0055] Step 1: Directly synthesizing a one-dimensional ultrafine Pt-Se-M nanomaterial (M = one or more of Cd, Zn, In, Pd, and Ni) by a one-pot wet chemical method.

[0056] Step 2: Obtaining a new Pt-based nanowire material by post-processing the Pt-Se-M nanowire or compounding it with other elements.

[0057] In step 1, the one-pot wet chemical method for synthesizing the one-dimensional ultrafine Pt-Se-M nanowire material is as follows:

[0058] S1. Preparing a mixed solution using a Pt precursor, a Se precursor, an M precursor, a reducing agent, and a solvent.

[0059] S2. Placing the obtained mixed solution in a container for ultrasonic dispersion until uniform to obtain a dispersion liquid.

[0060] S3. Sealing the container containing the dispersion liquid in step S2, heating it to 200-250°C, and maintaining the temperature for more than 3 hours to obtain a colloidal reaction product.

[0061] S4. Ultrasonically washing and centrifuging the obtained colloidal reaction product based on a mixed solution of ethanol and cyclohexane to obtain a one-dimensional ultrafine Pt-Se-M nanomaterial.

[0062] Further, in step S1, the following molar amounts are prepared and fed:

[0063] Pt precursor: Se precursor = 10: (1-4);

[0064] Pt precursor: M precursor = 10: (1-4);

[0065] Pt precursor: reducing agent = 1: (16-30).

[0066] In step S1, at least one of the following reducing agents is used in the method:

[0067] (1) no reducing agent;

[0068] (2) ascorbic acid;

[0069] (3) glucose;

[0070] (4) borane pinacol complex;

[0071] (5) benzoic acid;

[0072] (6) m-trihydroxybenzene;

[0073] (7) vitamin C.

[0074] In step S1, at least one of the following solvents is used in the method:

[0075] (1) oleylamine;

[0076] (2) oleic acid;

[0077] (3) 1-octadecene.

[0078] In step S1, the Pt precursor is one or more of acetylacetone platinum, potassium hexachloroplatinate, platinum chloride, potassium hexabromoplatinate, potassium chloroplatinate, and platinum bromide.

[0079] In step S1, the Se precursor is one or more of dibenzyl diselenide, selenium dioxide, selenium acid, selenium powder, and potassium selenite.

[0080] Further, the one-dimensional ultrafine Pt-Se-M nanomaterial prepared in step S4 has a Pt content of (35-70) at. % and a Se content of (12-25) at. % in terms of atomic percentage content of the contained elements.

[0081] In step two, the above post-treatment method is one of the following:

[0082] (1) The Pt-Se-M material obtained in step one is processed from top to bottom to remove, reduce or change a certain element in Pt-Se-M. The processing methods include: chemical etching, electrochemical etching, high-temperature evaporation based on the difference in element vapor pressure, and substitution reaction between the newly added element and the element in Pt-Se-M based on the difference in reduction potential.

[0083] (2) The Pt-Se-M nanowires obtained in step one were used as morphology templates. That is, after the synthesis in step one, a new elemental precursor was introduced, and the synthesis reaction was continued under certain temperature and reducing agent conditions. After the reaction was completed, the sample was cleaned and collected.

[0084] (3) To prepare Pt-Se-M multi-component ultrafine Pt-based nanomaterials, other elemental precursors N (N number ≥ 1) are introduced into the Pt-Se-M synthesis formulation. Specifically, in step S1, based on the synthesis of the Pt precursor, Se precursor, and M precursor, elemental N precursor is introduced to form a mixed solution, which is then ultrasonically dispersed in a container until homogeneous. Subsequent steps are the same as those for Pt-Se-M.

[0085] Furthermore, this invention provides a multi-component ultrafine Pt-based nanowire material prepared by the above-described method. The phase structure of this multi-component Pt-based nanomaterial is at least one of an alloy phase, an intermetallic compound phase, or an amorphous phase.

[0086] Furthermore, Pt-Se-M ultrafine nanowire materials and other ultrafine Pt-based nanowire materials obtained based on Pt-Se-M all have a curved worm-like nanowire morphology; have an ultrafine diameter of 0.5–4 nm; and have an aspect ratio of not less than 10 / 1.

[0087] Preferably, the nanowire has a diameter of 1 to 3 nm.

[0088] Furthermore, the nanowires are rich in defects, including at least one of the following defect types:

[0089] (1) Vacancy and interstitial atoms;

[0090] (2) Surface corner atoms and step atoms;

[0091] (3) Lattice distortion;

[0092] (4) Dislocation;

[0093] (5) Interface.

[0094] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of the present application. The experimental methods not specified in the following embodiments are usually performed according to conventional conditions or according to the conditions recommended by the manufacturers. Unless otherwise specified, all percentages, ratios, proportions or parts are by weight.

[0095] Embodiment 1

[0096] A preparation method of a multi-component ultrafine Pt-based nanowire material, as shown in Figure 1 , the multi-component ultrafine Pt-based nanowire material is formed by compounding other elements after etching and other post-processing based on a one-dimensional ultrafine Pt-Se-Cd nanomaterial, so as to obtain a multi-component ultrafine Pt-based nanowire material having the same morphology as the one-dimensional ultrafine Pt-Se-Cd nanomaterial;

[0097] One-pot wet chemical synthesis of a one-dimensional ultrafine Pt-Se-Cd nanomaterial, as shown in Figure 1 , the specific synthesis steps are as follows:

[0098] Step S1: 10 mg of platinum acetylacetone, 1.5 mg of dibenzyl diselenide, 2.3 mg of cadmium acetate dehydrate, 60 mg of glucose and 5 mL of oleylamine are weighed according to the ratio and placed in a 30 mL reaction bottle to prepare a mixed solution;

[0099] Step S2: the mixed solution obtained in step S1 is placed in a container and ultrasonically dispersed until uniform to obtain a dispersion liquid;

[0100] Step S3: the container containing the dispersion liquid in step S2 is sealed, and ultrasonic treatment is performed for 1 h after sealing, until the reactants are uniform, and then the reaction bottle is placed in an oil bath at 230℃ for reaction for 9 h. After the reaction is completed, it is cooled to room temperature to obtain a colloidal reaction product;

[0101] Step S4: the colloidal reaction product obtained in step S3 is placed in a mixed solution formed by cyclohexane and ethanol (V:V=1:8) for ultrasonic washing and centrifugation to obtain a one-dimensional ultrafine Pt-Se-Cd nanomaterial.

[0102] The obtained one-dimensional ultrafine Pt-Se-Cd nanomaterial, with reference to Figure 2 , Figure 3 , Figure 4 , Figure 5 , Figure 6 , Figure 7 , Figure 12 , Figure 13, with the following characteristics:

[0103] The worm-like bent nanowires are clearly visible Figure 2 a,b);

[0104] The average diameter size is 1.96±0.1 nm Figure 2 c);

[0105] The elements Pt, Se and Cd exist in the material, and the three are uniformly distributed in the material Figure 3 , Figure 4 );

[0106] The nanowire material is a multi-component alloy phase of face-centered cubic structure Figure 5 , Figure 6 );

[0107] The bent morphology of the nanowires results in a large number of low-coordination defect sites in the material, and there are obvious grain boundary defects in the material Figure 6 )。

[0108] Removing the Cd precursor or the Se precursor in the Pt-Se-Cd nanowire synthesis formula, while keeping other synthesis conditions unchanged, cannot obtain a nanowire structure; the synthesis of the nanowires is the result of the synergistic chemical action of the Pt, Se and Cd precursors Figure 7 )。

[0109] The Pt-Se-Cd nanowires are loaded on a carbon carrier (VXC-72) to prepare a catalyst, and are used for the common anode methanol oxidation reaction (MOR) of a direct methanol fuel cell. Under 0.1M HClO4+0.5M methanol electrolyte, the methanol oxidation peak of the Pt-Se-Cd nanowires is obviously higher than that of Pt / C, and the MOR mass activity is 3.59 times that of commercial Pt / C; at the same time, after a 7200s stability test, the activity of the Pt-Se-Cd nanowires is still higher than that of Pt / C, indicating that it has excellent catalytic stability Figure 12 ) Under the same MOR test conditions, the catalytic activity of the known Pt-based alloy nanowire catalyst is not as good as that of the Pt-Se-Cd ultrafine alloy nanowires involved in the present application (Table 1).

[0110] Table 1

[0111]

[0112]

[0113] Example 2

[0114] A method for preparing a multi-component ultrafine Pt-based nanowire material, as shown in Figure 1As shown, the multi-component ultrafine Pt-based nanowire material is formed by etching and other post-processing of the one-dimensional ultrafine Pt-Se-In nanomaterial and compounding with other elements, so as to obtain the multi-component ultrafine Pt-based nanowire material having the same morphology as the one-dimensional ultrafine Pt-Se-In nanomaterial.

[0115] One-pot wet chemical synthesis of the one-dimensional ultrafine Pt-Se-In nanomaterial, as shown in the following figure: Figure 1 As shown, the specific synthesis steps are as follows:

[0116] Step S1: 10 mg of platinum acetylacetone, 1.5 mg of dibenzyl diselenide, 2.5 mg of indium acetate, 60 mg of glucose and 5 mL of oleylamine are weighed according to the ratio and placed in a 30 mL reaction bottle to prepare a mixed solution;

[0117] Step S2: The mixed solution obtained in step S1 is placed in a container and ultrasonically dispersed until uniform to obtain a dispersion liquid;

[0118] Step S3: The container containing the dispersion liquid in step S2 is sealed, and after sealing, ultrasonic treatment is performed for 1 h until the reactants are uniform. Then, the reaction bottle is placed in an oil bath at 230°C and reacted for 9 h. After the reaction is completed, it is cooled to room temperature to obtain a colloidal reaction product;

[0119] Step S4: The colloidal reaction product obtained in step S3 is placed in a mixed solution of cyclohexane and ethanol (V:V=1:8) and ultrasonically washed and centrifuged to obtain the one-dimensional ultrafine Pt-Se-In nanomaterial.

[0120] The obtained one-dimensional ultrafine Pt-Se-In nanomaterial, with reference to Figure 8 , has the following characteristics:

[0121] It presents an ultrafine worm-like structure;

[0122] The average diameter size is 2.32±0.05 nm.

[0123] The Pt-Se-In nanowire is loaded on a carbon carrier (VXC-72) to prepare a catalyst, which is used for the common anode ethanol oxidation reaction (EOR) of direct ethanol fuel cell Figure 13 Under 0.1M HClO4+0.5M ethanol electrolyte, the ethanol oxidation peak of the Pt-Se-In nanowire is obviously higher than that of Pt / C, and the EOR mass activity is 1.41 Amg Pt -1 , which is 2.88 times that of commercial Pt / C.

[0124] Example 3

[0125] A preparation method of a multi-component ultrafine Pt-based nanowire material, as shown in Figure 1As shown, the multi-component ultrafine Pt-based nanowire material is formed by etching and other post-processing of the one-dimensional ultrafine Pt-Se-Zn nanomaterial and compounding with other elements, so as to obtain the multi-component ultrafine Pt-based nanowire material having the same morphology as the one-dimensional ultrafine Pt-Se-Zn nanomaterial.

[0126] One-pot wet chemical synthesis of the one-dimensional ultrafine Pt-Se-Zn nanomaterial is as shown in the following formula: Figure 1 As shown, the specific synthesis steps are as follows:

[0127] Step S1: 10 mg of platinum acetylacetone, 1.5 mg of dibenzyl diselenide, 1.9 mg of zinc acetate, 31 mg of borane-morpholine complex and 5 mL of oleylamine were weighed according to the ratio and placed in a 30 mL reaction bottle to prepare a mixed solution;

[0128] Step S2: The mixed solution obtained in step S1 was placed in a container and ultrasonically dispersed until uniform to obtain a dispersion liquid;

[0129] Step S3: The container containing the dispersion liquid in step S2 was sealed, and after sealing, ultrasonic treatment was performed for 1 h until the reactants were uniform. Then, the reaction bottle was placed in an oil bath at 230°C and reacted for 9 h. After the reaction was completed, the reaction product was cooled to room temperature to obtain a colloidal reaction product;

[0130] Step S4: The colloidal reaction product obtained in step S3 was placed in a mixed solution of cyclohexane and ethanol (V:V = 1:8) and ultrasonically washed and centrifuged to obtain the one-dimensional ultrafine Pt-Se-Zn nanomaterial.

[0131] The obtained one-dimensional ultrafine Pt-Se-Zn nanomaterial has the following characteristics, which are shown in the following formula: Figure 9

[0132] It presents an ultrafine worm-like structure;

[0133] The average diameter size thereof is 1.48±0.05 nm.

[0134] Example 4

[0135] A preparation method of a multi-component ultrafine Pt-based nanowire material is as shown in the following formula: Figure 1 As shown, the multi-component ultrafine Pt-based nanowire material is formed by etching and other post-processing of the one-dimensional ultrafine Pt-Se-Cd-In-Zn nanomaterial and compounding with other elements, so as to obtain the multi-component ultrafine Pt-based nanowire material having the same morphology as the one-dimensional ultrafine Pt-Se-Cd-In-Zn nanomaterial;

[0136] One-pot wet chemical synthesis of the one-dimensional ultrafine Pt-Se-Cd-In-Zn nanomaterial is as shown in the following formula: Figure 1 As shown, the specific synthesis steps are as follows: ​

[0137] Step S1: 10 mg of platinum acetylacetonate, 1.5 mg of dibenzyl diselenide, 0.9 mg of zinc acetate, 1.2 mg of indium acetate, 1.0 mg of cadmium acetate dihydrate, 120 mg of glucose and 5 mL of oleylamine were weighed according to the proportion and placed in a 30 mL reaction bottle to prepare a mixed solution;

[0138] Step S2: The mixed solution obtained in step S1 was placed in a container and ultrasonically dispersed until uniform to obtain a dispersion liquid;

[0139] Step S3: The container containing the dispersion liquid in step S2 was sealed, and after sealing, ultrasonic treatment was performed for 1 h until the reactants were uniform. Then, the reaction bottle was placed in an oil bath at 230°C for reaction for 9 h. After the reaction was completed, it was cooled to room temperature to obtain a colloidal reaction product;

[0140] Step S4: The colloidal reaction product obtained in step S3 was placed in a mixed solution of cyclohexane and ethanol (V:V = 1:8) for ultrasonic washing and centrifugation to obtain a one-dimensional ultrafine Pt-Se-Cd-In-Zn nanomaterial.

[0141] The obtained one-dimensional ultrafine Pt-Se-Cd-In-Zn nanomaterial, with reference to Figure 10 , has the following characteristics:

[0142] It presents an ultrafine worm-like structure.

[0143] Example 5

[0144] A preparation method of a multi-component ultrafine Pt-based nanowire material, as shown in Figure 1 , the multi-component ultrafine Pt-based nanowire material is obtained by etching and other post-processing of a one-dimensional ultrafine Pt-Se-Cd nanomaterial and compounding with other elements to obtain a multi-component ultrafine Pt-based nanowire material with the same morphology as the one-dimensional ultrafine Pt-Se-Cd nanomaterial;

[0145] One-pot wet chemical synthesis of one-dimensional ultrafine Pt-Se-Cd nanomaterial, as shown in Figure 1 , the specific synthesis steps are as follows:

[0146] Step S1: 100 mg of platinum acetylacetonate, 15 mg of dibenzyl diselenide, 25 mg of cadmium acetate dihydrate, 600 mg of glucose and 80 mL of oleylamine were weighed according to the proportion to prepare a mixed solution;

[0147] Step S2: The mixed solution obtained in step S1 was placed in a 500 mL reactor and ultrasonically dispersed until uniform. The reactor was placed in an oil bath at 230°C for reaction for 9 h. After the reaction was completed, it was cooled to room temperature to obtain a colloidal reaction product;

[0148] Step S3: the colloidal reaction product obtained in step S2 is placed in a mixed solution of cyclohexane and ethanol (V:V=1:8) for ultrasonic washing and centrifugation to obtain one-dimensional ultrafine Pt-Se-Cd nanomaterials.

[0149] The obtained one-dimensional ultrafine Pt-Se-Cd nanomaterials, with reference to Figure 11 , have the following characteristics:

[0150] The one-dimensional ultrafine Pt-Se-Cd nanomaterials have an ultrafine worm-like structure.

[0151] It can be seen from this embodiment 5 that the multi-component ultrafine Pt-based nanomaterial production technology has good industrialization potential.

[0152] Finally, it should be noted that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features, as long as they are within the spirit and principles of the present application. Any modification, equivalent replacement, improvement, etc. made shall be included in the protection scope of the present application.

Claims

1. A method for preparing a multi-component ultrafine Pt-based nanowire material, characterized in that, The multi-component ultrafine Pt-based nanowire material is based on one-dimensional ultrafine Pt-Se-M nanomaterials, and is obtained by post-processing or compounding with other elements. The multi-component ultrafine Pt-based nanowire material has a curved worm-like nanowire morphology, and is in any one of a single dispersion state, a branched state formed by nanowire bridging, and a network state formed by nanowire bridging. The multi-component ultrafine Pt-based nanowire material has an ultrafine diameter of 0.5-4 nm, and a length / diameter ratio of not less than 10 / 1. The multi-component ultrafine Pt-based nanowire material is rich in a large number of defects inside, and at least includes one of the following defect types: vacancies, interstitial atoms, lattice distortion, dislocations, and interfaces. The post-processing method includes a chemical etching method, an electrochemical etching method, high-temperature element evaporation based on vapor pressure difference, and a displacement reaction or a synthesis reaction based on a reduction potential difference. The one-dimensional ultrafine Pt-Se-M nanomaterial is synthesized by one-pot wet chemical method from a Pt precursor, a Se precursor, an M precursor, a reducing agent, and a solvent. The molar ratio of the Pt precursor, the Se precursor, the M precursor, and the reducing agent is as follows: The M precursor contains one or more of Cd, Zn, In, Pd, and Ni. The one-pot wet chemical synthesis method includes the following steps: Step S1: The Pt precursor, the Se precursor, the M precursor, and the reducing agent are taken according to the above-mentioned ratio, and are placed in a solvent to prepare a mixed solution. Step S2: The mixed solution obtained in step S1 is placed in a container and is ultrasonically dispersed to be uniform to obtain a dispersion liquid. Step S4: The colloidal reaction product obtained in step S3 is ultrasonically washed and centrifuged based on a mixed liquid formed by ethanol and cyclohexane to obtain the one-dimensional ultrafine Pt-Se-M nanomaterial. In step S1, the Pt precursor is one or more of platinum acetylacetonate, potassium hexachloroplatinate, platinum chloride, potassium hexabromoplatinate, potassium chloroplatinate, and platinum bromide. Step S3: The container containing the dispersion in step S2 is sealed and heated to 200 o C~250 o C, and kept for 3 hours or more to obtain a colloidal reaction product; In step S1, the Se precursor is one or more of dibenzyl diselenide, selenium dioxide, selenium acid, selenium powder, and potassium selenite.

2. The method for preparing multi-component ultrafine Pt-based nanowire materials according to claim 1, characterized in that, In step S1, the reducing agent is one or more of ascorbic acid, glucose, borane pinacol complex, benzoic acid, m-trihydroxybenzene, and vitamin C.

3. The method for preparing multi-component ultrafine Pt-based nanowire materials according to claim 1, characterized in that, The multi-component ultrafine Pt-based nanowire material is prepared by the multi-component ultrafine Pt-based nanowire material preparation method of any one of claims 1-4.

4. The method for preparing multi-component ultrafine Pt-based nanowire materials according to claim 1, characterized in that, The multi-component ultrafine Pt-based nanowire material contains Pt in a molar content of 35 at.%-70 at.%, and contains Se in a molar content of 12 at.%-25 at.%.

5. A multi-component ultrafine Pt-based nanowire material, characterized in that, ​ 6. The multi-component ultrafine Pt-based nanowire material of claim 5, wherein, ​

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