Preparation method and application of rubber shell-like PtBi electrocatalyst

Abstract

The present invention discloses a method for preparing a rubber-shell PtBi electrocatalyst and its application. A simple one-pot method without surfactant is used to prepare a PtBi electrocatalyst with a clean surface and a hollow rubber shell. The size of the obtained rubber shell structure is about 105nm. This special hollow rubber shell structure can expose more active sites, thereby improving the catalytic performance of the electrocatalyst. The cheap oxygen-philic metal Bi is alloyed with the noble metal Pt, which reduces the cost and makes the PtBi electrocatalyst prepared by the present invention show higher catalytic performance for ethylene glycol oxidation reaction than commercial Pt / C.

Description

Technical Field

[0001] The invention belongs to the field of electrocatalysis of fuel cells, and in particular relates to a preparation method of a rubber shell-shaped PtBi electrocatalyst and application thereof. Background Art

[0002] Direct alcohol fuel cells (DAFCs) play an important role in solving energy crises and environmental pollution problems due to their advantages of low cost, safety, high efficiency, easy storage and transportation. Liquid fuels usually use small organic alcohols, such as methanol and ethanol, which have been widely reported in direct alcohol fuel cells. However, ethylene glycol has a higher boiling point and energy density, as well as a faster electron transfer rate, which has attracted widespread attention in direct ethylene glycol fuel cells (DEGFCs). However, the oxidation of ethylene glycol at the anode is a complex and slow kinetic process, which greatly limits its development. As an anode catalyst, platinum (Pt) exhibits excellent catalytic activity in alkaline media. However, Pt-based catalysts still have problems such as high cost, poor durability and weak resistance to CO. In this context, a large number of studies have focused on developing a high-performance, low-cost Pt-based catalyst.

[0003] A large number of studies have shown that combining Pt with another metal (such as transition metals, rare earth metals, etc.) to form an alloy is a feasible and effective strategy. This is because the alloy can promote the reduction of the d-band center shift, improve the surface electronic environment, and is conducive to the improvement of electrocatalytic performance. For example, Yang et al. developed a simple tert-butyl alcohol-assisted structural reconstruction strategy to synthesize hierarchical porous high-alloyed PtNi nanoframe electrocatalyst (PtNiNF-NGA) on N-doped graphene aerogel, which has excellent catalytic activity for methanol oxidation under acidic conditions (1647mAmg Pt -1 ) and outstanding durability (Angew. Chem. Int. Ed. 2021, 60(17), 9590-9597). Zhu et al. synthesized one-dimensional ultrathin intermetallic compound Pt3Sn nanofibers by a simple one-pot method and demonstrated their enhanced electrocatalytic performance for ethanol oxidation reaction (EOR), ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR) (ACS Catal. 2020, 10(5), 3455-3461). Li et al. synthesized PtCu nanostar electrocatalysts by a simple solvothermal method, exposing copper-rich (110) crystal faces, and had high catalytic activity for the electrocatalytic oxidation of methanol and ethanol (Nano Res. 2019, 12(5), 1147-1153).

[0004] Adjusting the unique nanostructure morphology of Pt-based catalysts is also a key factor in improving their catalytic performance. For example, Fang et al. used CuNi octahedron as a template and synthesized CuNi@Pt-Cu core@shell nanooctahedrons through a colloidal seed-mediated method, which can promote the catalytic activity of methanol oxidation reaction (MOR) under acidic conditions (Angew. Chem. Int. Ed. 2021, 60 (14), 7675-7680). Zhang et al. first synthesized a well-crystallized lotus-thalamus-shaped Pt-Ni anisotropic superstructure with a platinum-rich surface and hexagonal close-packed / face-centered cubic (hcp / fcc) crystal phase through a simple one-pot solvothermal method. Compared with commercial Pt / C and other reported electrocatalysts, the synthesized Pt-NiASs showed excellent electrocatalytic activity and stability for hydrogen evolution reaction (HER) under alkaline conditions (Adv. Mater. 2018, 30 (30), 1801741). Dong et al. reported the synthesis of ultrathin PtRu nanocrystals with tunable morphologies (nanowires, nanorods, and nanocubes) by a one-step solvothermal method, and systematically studied the structure-directed effects and formation mechanisms of different surfactants through control experiments and time-dependent studies (J. Am. Chem. Soc. 2018, 140(3), 1142-1147). In addition, they evaluated the facet-dependent MOR electrocatalytic activity of PtRu catalysts for the first time by manipulating the exposed {111} / {100} facets on the surface of uniform nanocrystals. Surprisingly, {111}-capped PtRu nanowires exhibited higher stability and electrocatalytic mass activity for MOR, which were 2.28 and 4.32 times that of {100}-capped PtRu nanocubes and commercial Pt / C, respectively, indicating that PtRu {111} facets have superior methanol oxidation activity and CO poisoning resistance relative to {100} facets. Their work provides a new strategy for the synthesis of PtRu nanowires with unique spatial structures, which will promote their application prospects in catalytic reactions. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a rubber-shell PtBi electrocatalyst and its application to achieve efficient electrocatalytic oxidation of ethylene glycol. The present invention adopts a simple surfactant-free one-pot method to prepare a hollow rubber-shell PtBi electrocatalyst with a clean surface, and the size of the obtained rubber-shell structure is about 105nm. This special hollow rubber-shell structure can expose more active sites, thereby improving the catalytic performance of the electrocatalyst. Compared with commercial Pt / C, the PtBi electrocatalyst prepared by the present invention exhibits higher catalytic performance for ethylene glycol oxidation reaction.

[0006] The preparation method of the rubber shell-like PtBi electrocatalyst of the present invention comprises the following steps:

[0007] Step 1: Pt acetylacetonate and oxophilic metal Bi nitrate are used as alloy precursors, placed in a reactor with a certain amount of reducing agent, and a mixed solution of acetic acid and N,N-dimethylformamide is added as a solvent, and ultrasonically dissolved to form a uniformly dispersed mixed solution;

[0008] Step 2: heating the mixed solution obtained in step 1 from room temperature to 130°C to 160°C and reacting for 5 to 60 minutes; naturally cooling to room temperature after the reaction, washing with ethanol solution, centrifuging several times, and finally obtaining a hollow rubber shell-shaped PtBi nanocatalyst with a clean surface;

[0009] Step 3: Place the activated carbon in cyclohexane for ultrasonic dispersion, add the hollow rubber shell-shaped PtBi nanocatalyst obtained in step 2, continue to disperse evenly by ultrasonication, wash and centrifuge with a mixed solution of acetic acid and ethanol, and dry to obtain a hollow rubber shell-shaped PtBi / C electrocatalyst. The loading amount of the precious metal Pt is between 10% and 15%, and the loading amount of Bi is between 13% and 18%.

[0010] In the alloy precursor, the ratio of the acetylacetonate of Pt to the nitrate of the oxophilic metal Bi is 3.4:1 to 1:2.8, preferably 1:1, based on the molar ratio of Pt to Bi.

[0011] The volume ratio of acetic acid to N,N-dimethylformamide in the mixed solution of acetic acid and N,N-dimethylformamide is 1:3 to 1:6, preferably 1:4.

[0012] The reducing agent is tungsten hexacarbonyl, and the amount of the reducing agent added is sufficient to reduce the metal. Then, the proportion of the metal precursor and the proportion of the solvent are adjusted to adjust the morphology and performance.

[0013] The rubber-shell PtBi electrocatalyst of the present invention is used as a high-efficiency electrocatalyst in the process of electrocatalytic oxidation of ethylene glycol under alkaline conditions.

[0014] Specifically, a standard three-electrode system was used, with a glassy carbon electrode coated with a hollow rubber shell-shaped PtBi / C nanocatalyst as the working electrode, a platinum sheet electrode as the counter electrode, and a Hg / HgO electrode as the reference electrode. The ethylene glycol oxidation performance of the PtBi / C nanocatalyst was tested in an alkaline electrolyte, and PtBi / C was used as an anode electrocatalyst and commercial Pt / C as a cathode electrocatalyst in an alkaline ethylene glycol fuel cell. Cyclic voltammetry tests were performed at a scan rate of 50mV / s in the potential range of -0.9 to 0.3V, and compared with commercial Pt / C to explore the changes in its electrocatalytic performance.

[0015] The alkaline solution is a 1 mol / L KOH solution, and the molar ratio of KOH to (CH2OH)2 is 1:1.

[0016] The beneficial effects of the present invention are embodied in:

[0017] The hollow rubber shell-shaped PtBi / C nanocatalyst of the present invention is synthesized by a simple one-pot method, and provides a simple and convenient method for synthesizing a hollow structure. The present invention adopts a cheap precursor salt of the oxygen-philic metal Bi, and promotes the electrocatalytic activity of the catalyst through the electronic and synergistic effects between atoms under the premise of reducing the reaction cost. The catalyst of the present invention shows better battery performance in an actual direct ethylene glycol fuel cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and embodiments. It should be noted that these drawings do not limit the scope of the present invention, but are only used as an explanation of the technical solution of the present invention.

[0019] Figure 1 This is a transmission electron microscope image (TEM) of the PtBi nanocatalyst prepared in Example 1.

[0020] Figure 2 This is the X-ray diffraction pattern (XRD) of the PtBi nanocatalyst prepared in Example 1.

[0021] Figure 3 This is a comparison diagram of the cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 1 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0022] Figure 4 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 1 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0023] Figure 5 The PtBi / C nanocatalyst prepared in Example 1 was used as an anode catalyst and commercial Pt / C was used as a cathode catalyst in an alkaline ethylene glycol fuel cell (6 mol / LKOH+3 mol / L(CH2OH)2-O2), and the performance of the battery at different temperatures was studied.

[0024] Figure 6 The PtBi / C nanocatalyst prepared in Example 1 was used as an anode catalyst and commercial Pt / C was used as a cathode catalyst in an alkaline ethylene glycol fuel cell (6 mol / LKOH+3 mol / L(CH2OH)2-air), and the battery performance at 80°C was studied.

[0025] Figure 7This is a comparison diagram of the cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 2 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0026] Figure 8 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 2 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0027] Fig. 9 This is a comparison diagram of the cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 3 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0028] Fig.10 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 3 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0029] Fig.11 This is a comparison diagram of the cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 4 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0030] Fig.12 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 4 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0031] Fig.13 This is a comparison diagram of the cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 5 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0032] Fig.14 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 5 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2.

[0033] Fig.15 This is a transmission electron microscope image of the PtBi / C nanocatalyst prepared in Example 6.

[0034] Fig.16 This is a transmission electron microscope image of the PtBi / C nanocatalyst prepared in Example 7. DETAILED DESCRIPTION

[0035] The technical scheme of the present invention is further described below in conjunction with specific embodiments. It should be noted that the specific description of the embodiments below is only used to illustrate the synthesis, characterization and performance of the catalyst and should not be construed as a limitation of the present invention. Embodiments not directly mentioned in this article may still be obtained by combining these technical schemes.

[0036] Embodiment 1:

[0037] The preparation method of the hollow rubber shell-shaped PtBi / C electrocatalyst with clean surface in this embodiment comprises the following steps:

[0038] 1. Weigh 5.0 mg Pt(acac)2, 6.2 mg Bi(NO3)3·5H2O and 30 mg W(CO)6 into a glass bottle, add 2 mL acetic acid and 8 mL N,N-dimethylformamide, cover the bottle tightly, and ultrasonicate for about 10 minutes until the precursor is completely dissolved to form a uniform mixture.

[0039] 2. Place the above mixture in an oil bath, heat from room temperature to 140°C, and maintain for 15 minutes.

[0040] 3. After the reaction is completed, cool naturally to room temperature, wash with ethanol solution, collect the product by centrifugation at 9000 rpm, repeat the operation three times, and dissolve the obtained product in 5 mL of cyclohexane for later use.

[0041] 4. Weigh 7.0 mg of activated carbon into a centrifuge tube, add 5 mL of cyclohexane and sonicate for 30 minutes to evenly disperse the activated carbon.

[0042] 5. Add the product obtained in step 3 to the activated carbon dispersed in step 4, ultrasonicate for 1 hour, centrifuge, wash once with a mixed solution of acetic acid and ethanol, and then wash once with ethanol. After the product is dried, a hollow rubber shell-shaped PtBi / C electrocatalyst with a clean surface can be obtained.

[0043] Figure 1 This is a TEM image of the PtBi nanocatalyst prepared in Example 1. It can be seen from the image that PtBi presents a hollow rubber shell structure.

[0044] Figure 2 This is the XRD pattern of the PtBi nanocatalyst prepared in Example 1. It can be seen from the figure that the XRD diffraction peak of the sample corresponds to PtBi (ICSD: 58845), indicating the successful synthesis of the PtBi intermetallic compound.

[0045] Figure 3The cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 1 and commercial Pt / C in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2 are compared. It can be seen from the figure that the commercial Pt / C (1.82Amg Pt -1 ) compared with the prepared PtBi / C catalyst, which showed higher catalytic oxidation activity of ethylene glycol, and its mass activity reached 22.44Amg Pt -1 , which is about 12.33 times that of commercial Pt / C. These results indicate that the PtBi / C nanocatalyst prepared in Example 1 has better ethylene glycol oxidation performance.

[0046] Figure 4 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 1 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2. It can be seen from the figure that compared with the commercial Pt / C, the PtBi / C nanocatalyst prepared in Example 1 still has a higher mass activity after a stability test of 2000 s, indicating that the prepared PtBi / C electrocatalyst has better stability and is suitable for long-term operation.

[0047] Figure 5 The PtBi / C nanocatalyst prepared in Example 1 was used as the anode catalyst and the commercial Pt / C was used as the cathode catalyst in an alkaline ethylene glycol fuel cell (6 mol / L KOH+3 mol / L (CH2OH)2-O2), and the performance of the battery at different temperatures was studied. Figure 6 It can be seen that with the increase of temperature, the peak power density of the prepared PtBi / C increases. When the temperature reaches 80°C, the peak power density of PtBi / C is 98.11mWcm -2 , the current density is 416.67mAcm -2 .

[0048] Figure 6 The PtBi / C nanocatalyst prepared in Example 1 was used as the anode catalyst and the commercial Pt / C was used as the cathode catalyst in an alkaline ethylene glycol fuel cell (6 mol / L KOH+3 mol / L (CH2OH)2-air). Figure 7 It can be seen that when oxygen is replaced by air and the temperature is 80°C, the peak current density of PtBi / C is 72.74 mWcm -2 , the current density is 263.89mAcm -2 .

[0049] Embodiment 2:

[0050] A PtBi / C electrocatalyst with a clean surface and a hollow rubber shell shape was synthesized according to the preparation method described in Example 1, while keeping other conditions unchanged and only extending the oil bath time to 30 minutes.

[0051] Figure 7 The cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 2 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2 are compared. It can be seen from the figure that the commercial Pt / C (1.82Amg Pt -1 ) compared with the prepared PtBi / C catalyst, which showed higher catalytic oxidation activity of ethylene glycol, and its mass activity reached 14.90Amg Pt -1 , which is about 8.19 times that of commercial Pt / C. These results indicate that the PtBi / C nanocatalyst prepared in Example 2 has better ethylene glycol oxidation performance.

[0052] Figure 8 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 2 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2. It can be seen from the figure that compared with the commercial Pt / C, the PtBi / C nanocatalyst prepared in Example 2 still has a higher mass activity after 2000s of stability test, indicating that the prepared PtBi / C electrocatalyst has better stability.

[0053] Embodiment 3:

[0054] A hollow rubber shell-shaped PtBi / C electrocatalyst with a clean surface was synthesized according to the preparation method described in Example 1, keeping other conditions unchanged, and only adjusting the mass of Pt(acac)2 to 3.2 mg and the mass of Bi(NO3)3·5H2O to 8.0 mg.

[0055] Fig. 9 The cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 3 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2 are compared. It can be seen from the figure that the commercial Pt / C (1.82Amg Pt -1 ) compared with the prepared PtBi / C catalyst, which showed higher catalytic activity for ethylene glycol oxidation, and its mass activity reached 20.05Amg Pt -1 , which is about 11.02 times that of commercial Pt / C. These results indicate that the PtBi / C nanocatalyst prepared in Example 3 has better ethylene glycol oxidation performance.

[0056] Fig.10 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 3 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2. It can be seen from the figure that compared with the commercial Pt / C, the PtBi / C nanocatalyst prepared in Example 3 still has a higher mass activity after 2000s of stability test, indicating that the prepared PtBi / C electrocatalyst has better stability.

[0057] Embodiment 4:

[0058] A PtBi / C electrocatalyst with a clean surface and a hollow rubber shell shape was synthesized according to the preparation method described in Example 1, while keeping other conditions unchanged and only adjusting the mass of Bi(NO3)3·5H2O to 3.1 mg.

[0059] Fig.11 The cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 4 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2 are compared. It can be seen from the figure that the commercial Pt / C (1.82Amg Pt -1 ) compared with the prepared PtBi / C catalyst, which showed higher catalytic activity for ethylene glycol oxidation, and its mass activity reached 14.54Amg Pt -1 , which is about 7.99 times that of commercial Pt / C. These results indicate that the PtBi / C nanocatalyst prepared in Example 4 has better ethylene glycol oxidation performance.

[0060] Fig.12 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 4 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2. It can be seen from the figure that compared with the commercial Pt / C, the PtBi / C nanocatalyst prepared in Example 4 still has a higher mass activity after 2000s of stability test, indicating that the prepared PtBi / C electrocatalyst has better stability.

[0061] Embodiment 5:

[0062] A PtBi / C electrocatalyst with a clean surface and a hollow rubber shell shape was synthesized according to the preparation method described in Example 1, while keeping other conditions unchanged and only adjusting the mass of Bi(NO3)3·5H2O to 4.3 mg.

[0063] Fig.13The cyclic voltammetry curves of the PtBi / C nanocatalyst prepared in Example 5 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2 are compared. It can be seen from the figure that the commercial Pt / C (1.82Amg Pt -1 ) compared with the prepared PtBi / C catalyst, which showed higher catalytic activity for ethylene glycol oxidation, and its mass activity reached 12.08Amg Pt -1 , which is about 6.64 times that of commercial Pt / C. These results indicate that the PtBi / C nanocatalyst prepared in Example 5 has better ethylene glycol oxidation performance.

[0064] Fig.14 This is a comparison diagram of the chronoamperometric curves of the PtBi / C nanocatalyst prepared in Example 5 and the commercial Pt / C catalyst in a mixed electrolyte solution of 1 mol / L KOH and 1 mol / L (CH2OH)2. It can be seen from the figure that compared with the commercial Pt / C, the PtBi / C nanocatalyst prepared in Example 5 still has a higher mass activity after 2000s of stability test, indicating that the prepared PtBi / C electrocatalyst has better stability.

[0065] Embodiment 6:

[0066] A PtBi / C electrocatalyst with a clean surface and a hollow rubber shell shape was synthesized according to the preparation method described in Example 1, while keeping other conditions unchanged and adjusting only the amounts of acetic acid and N,N-dimethylformamide to 5 mL.

[0067] Fig.15 This is a transmission electron microscope image of the PtBi / C nanocatalyst prepared in Example 6. It can be seen from the figure that when the volume ratio of acetic acid and N,N-dimethylformamide is adjusted to 1:1, the morphology and structure of the PtBi / C catalyst changes.

[0068] Embodiment 7:

[0069] A PtBi / C electrocatalyst with a clean surface and a hollow rubber shell shape was synthesized according to the preparation method described in Example 1, while keeping other conditions unchanged and adjusting the amounts of acetic acid and N,N-dimethylformamide to 0 mL and 10 mL, respectively.

[0070] Fig.16 This is a transmission electron microscope image of the PtBi / C nanocatalyst prepared in Example 7. It can be seen from the figure that when the volumes of acetic acid and N,N-dimethylformamide are adjusted to 0 mL and 10 mL respectively, the morphology and structure of the PtBi / C catalyst changes.

Claims

1. A method for preparing a rubber-shell PtBi electrocatalyst using a surfactant-free one-pot process, characterized in that The steps include: Step 1: Pt acetylacetonate and oxophilic metal Bi nitrate are used as alloy precursors, placed in a reactor with a certain amount of reducing agent, and a mixed solution of acetic acid and N,N-dimethylformamide is added as a solvent, and ultrasonically dissolved to form a uniformly dispersed mixed solution; Step 2: The mixed solution obtained in step 1 is heated from room temperature to 130°C to 160°C and reacted for 5 to 60 minutes; after the reaction is completed, it is naturally cooled to room temperature, washed with an ethanol solution, and centrifuged several times to finally obtain a hollow rubber shell-shaped PtBi nanocatalyst with a clean surface; Step 3: placing the activated carbon in cyclohexane for ultrasonic dispersion, adding the hollow rubber shell-shaped PtBi nanocatalyst obtained in step 2, continuing to disperse evenly by ultrasonic dispersion, washing and centrifuging with a mixed solution of acetic acid and ethanol, and drying to obtain a hollow rubber shell-shaped PtBi / C electrocatalyst; The reducing agent is tungsten hexacarbonyl.

2. The preparation method according to claim 1, characterized in that: In the alloy precursor, the ratio of the acetylacetonate of Pt to the nitrate of the oxophilic metal Bi is 3.4:1 to 1:2.8 according to the molar ratio of Pt to Bi.

3. The preparation method according to claim 2, characterized in that: The ratio of the acetylacetonate of Pt to the nitrate of the oxophilic metal Bi is 1:1 based on the molar ratio of Pt to Bi.

4. The preparation method according to claim 1, characterized in that: The volume ratio of acetic acid to N,N-dimethylformamide in the acetic acid and N,N-dimethylformamide mixed solution is 1:3-1:

6.

5. The preparation method according to claim 1, characterized in that: In the hollow rubber shell-shaped PtBi / C electrocatalyst, the loading amount of precious metal Pt is between 10% and 15%, and the loading amount of Bi is between 13% and 18%.

6. Use of the rubber-shell PtBi electrocatalyst prepared by any one of the preparation methods of claims 1 to 5, characterized in that: The rubber-shell PtBi electrocatalyst is used as a high-efficiency electrocatalyst in the process of electrocatalytic oxidation of ethylene glycol under alkaline conditions.

7. The use according to claim 6, characterized in that: A standard three-electrode system was used, with a glassy carbon electrode coated with a hollow rubber shell-shaped PtBi / C nanocatalyst as the working electrode, a platinum sheet electrode as the counter electrode, and a Hg / HgO electrode as the reference electrode, to carry out catalytic oxidation of ethylene glycol in an alkaline electrolyte.

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