Noble Metal-Loaded Multilayer Hollow Microsphere Liquid Metal-Based Catalyst and Preparation Method

Abstract

The present invention relates to a noble metal-loaded multi-layer hollow microsphere liquid metal-based catalyst and a preparation method thereof. By introducing a cationic surfactant to form a relatively stable LM-S + +M ‑ and LM@G-S + +M ‑ configuration intermediates, multi-layer hollow microspheres supported by a liquid metal structure are obtained, which can maintain their original morphology after long-term operation and have a large specific surface area. Among them, the construction of the LM@G-S + +M ‑ configuration intermediate is as follows: first, reduced graphene oxide is grown on the outer surface through the reducibility of liquid metal particles to form a stable core-shell structure of LM@G, and then a cationic surfactant is introduced to generate a more stable hollow microsphere composite electrocatalyst, thereby improving the stability and corrosion resistance of the catalyst. On this basis, M ‑ can also be extended to carry out reduction reactions with noble metal anion groups in metal salt solutions such as K2PtCl6, AuCl3HCl4H2O, and Na2PdCl4. The prepared catalyst has high catalytic activity and stability, exhibits excellent electrocatalytic performance, and shows broad application prospects in the field of electrocatalysis.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic chemistry, and particularly relates to a preparation method of a noble metal-loaded multi-layer hollow microsphere liquid metal-based catalyst. Background Art

[0002] Energy is the foundation of economic development. Without energy, there would be no modern civilization. There have been several industrial revolutions in history, each of which has promoted the development of human social civilization. Conventional fossil energy reserves are relatively limited and cause environmental pollution. In contrast, fuel cells have great advantages. Fuel cells can easily achieve the conversion of electrical energy to chemical energy, and electrocatalysts are an important way to promote the utilization rate of alcohols in the field of fuel cells. Preparing electrocatalysts with high activity and high stability is the main research direction of current alcohol fuel cells. Currently, the most commonly used is the platinum-based catalyst. Although platinum has high activity for electrocatalysis and can release protons and electrons at very low potentials, platinum is easily poisoned by adsorbed species generated during the reaction process, thus greatly weakening its catalytic effect. Moreover, the high price of platinum-based catalysts also greatly limits their commercial application in the field of electrocatalysis.

[0003] Currently, the methods for improving the performance of platinum-based catalysts can generally be divided into three categories. The first category is that usually, Pt is made into a Pt-M (Fe, Co, Ni, etc.) alloy catalyst, and the doping of non-precious metal elements is used to achieve the purpose of improving its activity and reducing costs. Secondly, research shows that the catalytic activity of metal particles not only depends on their elemental components, but also on the carrier of the particles, the elemental distribution state, and the morphological structure of the catalyst. Making the catalyst into special structures such as dendrites, nanoflowers, and spheres can enhance its catalytic activity. Thirdly, platinum-based catalysts are grown on the surface of the carrier. Common carriers include carbon materials such as carbon nanotubes and graphene, thereby improving their chemical stability and corrosion resistance. However, research shows that when Pt is unevenly distributed on the surface of the carrier, it will not only lead to insufficient synergy between Pt and the carrier, but also may cause Pt to fall off from the surface of the carrier after working for a period of time, thus greatly reducing its electrocatalytic activity.

[0004] As a post-transition metal (Ga, In, Sn), metallic gallium and its gallium-based liquid metal (LM) have a relatively low D-band center and small adsorption energy. After binding with Pt, it can effectively reduce the surface adsorption energy of Pt, thereby obtaining a composite electrocatalyst with high activity. For example, the Pt-Ga-based electrocatalyst developed by Ribeiro exhibits good catalytic performance in the ethanol oxidation reaction (EOR); Stasi et al. studied the high catalytic ability of Pt-Ga catalysts supported on multi-walled carbon nanotubes for the hydrogenation of citral to α-β unsaturated aldehydes. However, during the application process, it was found that there are some problems with the above catalysts. Since Pt is unevenly distributed on the surface of the support, the active sites cannot be fully exposed, which to a certain extent affects its working performance; in addition, the uneven loading structure will also cause Pt to be gradually peeled off during use, significantly shortening the catalyst life.

[0005] For the above reasons, the present invention utilizes the property that the LM has a high electrode potential and high metal activity and can be used as an effective reducing agent, and prepares a Pt-Ga-based catalyst through a galvanic displacement reaction. More ingeniously, in order to improve the uniformity of the reaction and growth of Pt on the surface of liquid Ga-based particles, we first introduce a cationic surfactant during the preparation process, so that the surface of Ga and Ga-based alloy particles is positively charged during the displacement reaction. Through electrostatic interaction, the acid radical ions of the precursor chloroplatinic acid (salt) are riveted on the surface of the liquid metal (alloy), so that Pt is uniformly distributed on the surface of the liquid metal after the displacement reaction, forming a stable multi-layer hollow microsphere loaded with precious metals, thereby improving the catalytic effect of the catalyst. The innovation of this method lies in generating relatively stable LM-S + +M - and LM@G-S + +M - configuration intermediates (where LM represents Ga or Ga-based liquid metal, S + represents a cationic surfactant, M - represents the anion of the precious metal salt, and G represents reduced graphene oxide), and then a stable multi-layer hollow microsphere liquid metal-based electrocatalyst loaded with precious metals is prepared.

[0006] The present invention introduces a cationic surfactant to form relatively stable LM-S + +M - and LM@G-S + +M - configuration intermediates, obtaining multi-layer hollow microspheres with liquid metal as the reducing agent and structural support agent, and the precious metal can stably exist on the surface of the liquid metal, maintaining its original morphology after long-term operation, and having a large specific surface area. Among them, LM@G-S + +M -The construction of the configuration intermediate is to first grow reduced graphene oxide on the outer surface through the reducing property of liquid metal particles to form a stable core-shell structure of LM@G, and then introduce a cationic surfactant, one end of which is adsorbed on the graphene through electrostatic compounding, and the positive charge at the other end can more firmly rivet the chloroplatinate ion to generate a more stable hollow microsphere composite electrocatalyst, thereby improving the stability and corrosion resistance of the catalyst. On this basis, M - It can also be extended to the reduction reaction with precious metal anion groups in metal salt solutions such as K2PtCl6, AuCl3HCl4H2O, and Na2PdCl4. The prepared multilayer hollow liquid metal-based catalyst with stable precious metal loading greatly improves the catalytic activity, catalytic stability and adsorption of precious metal elements, reduces costs, and exhibits excellent electrocatalytic performance, showing broad application prospects in the field of electrocatalysis. Summary of the invention

[0007] The present invention provides a method for preparing a precious metal-loaded multilayer hollow microsphere liquid metal-based catalyst. Compared with commercial platinum-carbon catalysts, the catalyst has greatly improved anti-poisoning and stability, and has reduced costs, and has significant advantages in the field of catalysis.

[0008] The liquid metal-based catalyst is realized by the following technical solution:

[0009] Using LM-S + +M - Preparation of LM@Pt by intermediate configuration:

[0010] Step 1: Preparation of surfactant solution: Select cationic surfactants such as hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium bromide (CTAC), hexadecylpyridinium chloride (CPC) that can be connected to LM through hydrogen bonds, or cationic surfactants such as sodium dodecyl sulfate (SDS), n-dodecyl mercaptan (C12) that can be connected to liquid metal through sulfur atoms, and prepare a solution with a concentration of 1 to 5 mg / mL, using a volume of 1 to 5 mL.

[0011] Step 2: Pretreatment of LM: Weigh 0.1-0.5 g of LM, melt it into liquid in a water bath, add 1-5 mL of the solution prepared in step 1 for dispersion, select 100-800 w of ultrasonic power, control the temperature at 0-10 ° C, and ultrasonic time for 1 h to obtain LM-S. + , freeze-drying;

[0012] Step 3: Preparation of LM@Pt: Weigh 0.1-0.5 g of dried LM and 2.5-10 mL of K2PtCl6, react at 25-50 °C for 2 h to obtain LM-S + +M- Type LM@Pt electrocatalyst.

[0013] Using LM@G-S + +M - Intermediate configuration to prepare LM@G-Pt:

[0014] Step 1: Dispersion of graphene oxide (GO): Weigh 1 - 5 mg of GO and 10 - 20 mL of DI water, and perform ultrasonic fragmentation. Disperse for a period of time under the condition of 100 - 800 w, and control the temperature at 0 - 10 °C to obtain a graphene solution with a concentration of 0.1 - 0.4 mg / mL.

[0015] Step 2: Preparation of LM@G: LM reduces GO (graphene oxide) to LM@G through an electroreplacement reaction. Calculate the mass of the graphene oxide solution to be 2 - 4 mg according to the solid-liquid ratio in Step 1, and calculate the mass ratio of LM to GO to be 6:3 - 6:1 according to its solid-liquid ratio, and mix according to this ratio. Add 2 - 5 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, and adjust the pH of the mixed solution to 1 - 3. One is to prevent the formation of a dense oxide film on the surface of liquid metal particles, and the other is to provide H + Guarantee. At room temperature, stir the reaction magnetically for 3 h, wash with water and dry to obtain LM@G.

[0016] Step 3: Preparation of cationic surfactant: Prepare an aqueous solution of poly(diallyldimethylammonium bromide) (PDDA), glutamic acid, and glycine with a concentration of 1 - 4 mg / mL.

[0017] Step 4: Preparation of LM@G-S + : Mix LM@G with the cationic surfactant at a volume ratio of 1:1 - 1:4, and react for 2 h. Centrifuge and collect, and after drying, obtain LM@G-S + And salts of other anions.

[0018] Step 5: Preparation of LM@G-M: Using LM@G-S + As a support template and sacrificial agent, react with 5 - 10 mL of an aqueous solution of precious metal salts such as 0.02 mol / L K2PtCl6, AuCl3HCl4H2O, and Na2PdCl4 to obtain the electrocatalyst LM@G-M.

[0019] The main characteristics of the electrocatalyst are as follows:

[0020] Using LM-S + +M - Intermediate configuration to prepare LM@M

[0021] The surfactant solution described in Step 1 is a cationic surfactant that can be connected to LM.

[0022] The liquid metal solution described in Step 2 can obtain uniformly dispersed liquid metal particles with a size of 100 - 300 nm.

[0023] The stable noble metal-loaded hollow multi-layer liquid metal-based catalyst described in Step 3 needs to react at 25 - 50 °C.

[0024] Using LM@G-S + +M - Prepare LM@G-M with the intermediate configuration:

[0025] The graphene oxide described in Step 1 needs to be dispersed under the condition of 100 - 800 w, and the temperature is 0 - 10 °C.

[0026] The uniformly dispersed liquid metal particles obtained from the liquid metal solution described in Step 2 can have their surfaces uniformly wrapped by graphene. The particle size is 100 - 300 nm. Graphene can react with LM only when the pH value is 1 - 2.

[0027] The surfactant solution described in Step 3 is a cationic surfactant that can combine with the positive and negative charges of reduced graphene. The concentration of the cationic surfactant solution is 1 - 4 mg / m.

[0028] The metal salt M in the noble metal-stably loaded hollow multi-layer liquid metal-based catalyst described in Step 5 - can be obtained from the salt solutions of K2PtCl6, AuCl3HCl4H2O, and Na2PdCl4.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] 1. Compared with the electrocatalysts for traditional synthetic alcohol fuel cells, its preparation conditions are mild, which is conducive to large-scale preparation. At the same time, the Pt element on the surface of the generated catalyst is uniformly distributed, and the overall structure of the catalyst is stable, which is beneficial to the improvement of the overall performance and the extension of the service life.

[0031] 2. Based on LM-S + +M - The hollow multi-layer hollow sphere electrocatalyst formed by the intermediate configuration can obtain a liquid metal-based catalyst with a large specific surface area and uniform size. The noble metal is uniformly distributed on the surface of the hollow microspheres. For the alcohol fuel cell catalyst, it can provide more active sites, thereby improving the conversion rate of alcohols; and based on LM@G-S + +M - Configuration, introducing physically and chemically stable and corrosion-resistant graphene as a carrier, improves the stability and corrosion resistance of the catalyst.

[0032] 3. Compared with commercial Pt / C, the LM@M and LM@G-M materials prepared by the present invention based on the configurations of LM-S + +M - and LM@G-S + +M - intermediates show a significant reduction in Pt consumption and a remarkable improvement in the electronic synergy effect. In addition, the introduction of graphene and LM greatly enhances the stability, corrosion resistance, and electron transfer efficiency of the catalyst, making it widely applicable to the catalytic fields of methanol, ethanol, and ethylene glycol fuel cells.

[0033] In summary, the present invention proposes a preparation method for a noble metal-loaded multi-layer hollow sphere liquid metal-based catalyst, which has the advantages of simple process, environmental friendliness, etc., and also provides a feasible approach for the controlled synthesis of multi-metal catalysts with special structures. Description of the Drawings

[0034] Figure 1 Morphological characteristics of the dispersed liquid metal; sub-micron liquid metal spheres were prepared, providing conditions for the next step of experiments.

[0035] Figure 2 FTIR test of the reduced LM / GO; Figures a, b, and c are the FITR spectra of GO, GO:L = 2:6, and GO:L = 3:6 (wt% ratio), respectively. The upper figure is the FTIR spectrum. According to the spectrum, the changes in functional groups before and after reduction are determined. The peak near 1729 cm-1 represents the C=O peak; the peaks at 1221, 1172, and 1053 cm-1 represent the C-O peak. Compared with commercial GO, the oxygen-containing groups gradually decrease, further proving the successful reduction of graphene oxide.

[0036] Figure 3 X-ray photoelectron spectroscopy of the reduced LM and GO; Figure b is GO:LM = 2:6 (wt%); Figure c is GO:LM = 3:6 (wt%). Compared with Figure a of GO, the C-O peak and C=O peak are significantly reduced, attributed to the decrease in oxygen-containing groups, indicating that the reduction effect of GO is achieved. Detailed Embodiments

[0037] In this experiment, the liquid metal was first mechanically dispersed by physical fragmentation, and then after the liquid metal interacted with a surfactant or graphene, it was replaced with a noble metal. The specific implementation steps are as follows:

[0038] Example 1: 0.1 g of Ga was melted and placed into a centrifuge tube. 5 mL of CTAB with a concentration of 1 mg / L was added for dispersion. The dispersion power was 100 W, the temperature was 0 °C, and ultrasonic treatment was carried out for 1 h to obtain a homogeneous solution. 2 mL of K2PtCl6 was added to the above solution, and after reacting for 2 h, centrifugation was performed. The centrifuged product was washed with ethanol and dried to obtain a hollow LM@Pt electrocatalyst.

[0039] Example 2: 0.1 g of Ga was melted and placed into a centrifuge tube. 5 mL of CTAC with a concentration of 1 mg / L was added for dispersion. The dispersion power was 400 W, the temperature was 0 °C, and ultrasonic treatment was carried out for 1 h to obtain a homogeneous solution. 2 mL of K2PtCl6 was added to the above solution, and after reacting for 1 h, centrifugation was performed. The centrifuged product was washed with ethanol and dried to obtain a hollow multi-layered LM@Pt.

[0040] Example 3: 0.1 g of Ga was weighed, melted into a liquid state, and placed into a centrifuge tube. 5 mL of CPC with a concentration of 1 mg / L was added for dispersion, and dispersion was carried out at a dispersion power of 600 W. The temperature was controlled at 0 °C, and ultrasonic treatment was carried out for 1 h. After the reaction, it was used as a homogeneous solution. 2 mL of K2PtCl6 was added to the above LM solution, and the reaction was carried out for 1 h. The product was collected by centrifugation, washed with ethanol, and dried to obtain a hollow LM@Pt.

[0041] Example 4: 0.1 g of Ga was weighed, melted into a liquid state, and placed into a centrifuge tube. 5 mL of an aqueous solution of C12 with a concentration of 1 mg / L was added for dispersion, and dispersion was carried out at a dispersion power of 800 W. The temperature was 0 °C, and ultrasonic treatment was carried out for 1 h. After the reaction, it was used as a homogeneous solution. 2 mL of K2PtCl6 was added to the above solution, and after reacting for 1 h, it was collected by centrifugation, washed with ethanol, and dried to obtain a hollow multi-layered LM@Pt.

[0042] Implementation Case 5: Weigh 0.1 g of Ga, melt it into a liquid state, put it into a centrifuge tube, add it to 50 mL of ethanol solution for dispersion. The ultrasonic power is 600 w, the ultrasonic time is 2 h, and the temperature is controlled at 5 °C. After the reaction, it is a uniform solution for standby; Weigh 2.5 mg of GO, add 15 mL of DI water, and perform ultrasonic fragmentation for 1 h. The power is 600 w, and the temperature is controlled at 5 °C. After dispersion, the graphene solution is 0.3 mg / mL. Take 15 mL of the aqueous solution of LM after ultrasonic treatment and the aqueous solution formed by GO. The mass ratio of LM to GO is 6:2. Add 10 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, adjust the pH to 2, and react at room temperature for 3 h under magnetic stirring. After the reaction, the measured pH is 4, which proves the smooth progress of the reduction, and LM@G is obtained; Take 180 mg of PDDA and 250 mg of NaCl, ultrasonically disperse them in 50 mL of water to form an aqueous solution of PDDA. Add LM@G to the above aqueous solution. After reacting for 2 h, add 2 mL of K2PtCl6, react for 1 h, centrifuge and collect, wash with ethanol, and dry to obtain the noble metal-stably loaded multi-layer hollow sphere LM@G-Pt catalyst.

[0043] Implementation Case 6: Weigh 0.1 g of Ga, melt it into a liquid state, put it into a centrifuge tube, add it to 50 mL of ethanol solution for dispersion. The ultrasonic power is 600 w, the ultrasonic time is 2 h, and the temperature is 5 °C. After the reaction, it is a uniform solution for standby; Weigh 2.5 mg of GO2.5, add 15 mL of DI water, and perform ultrasonic fragmentation for 1 h. The power is 600 w, and the temperature is controlled at 5 °C. After dispersion, the graphene solution is 0.3 mg / mL. Take 15 mL of the aqueous solution of LM after ultrasonic treatment and the aqueous solution formed by GO. The mass ratio of LM to GO is 6:2. Add 10 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, adjust the pH to 2, and react at room temperature for 3 h under magnetic stirring. After the reaction, the measured pH is 4, which proves the smooth progress of the reduction, and LM@G is obtained; Take 200 mg of glutamic acid and add 200 mL of water. Add LM@G to the above aqueous solution and react for 2 h. Centrifuge and collect, wash with ethanol, and dry to obtain the noble metal-stably loaded multi-layer hollow sphere LM@G-Pt catalyst.

[0044] Implementation Case 7: Weigh 0.1 g of Ga. After melting it into a liquid state, put it into a centrifuge tube and disperse it in 50 mL of ethanol solution. The ultrasonic power is 600 w, the ultrasonic time is 2 h, and the temperature is controlled at 5 °C. After the reaction, it is a uniform solution for standby; Weigh 2.5 mg of GO, add 15 mL of DI water and perform ultrasonic crushing for 1 h. The power is 600 w, and the temperature is controlled at 5 °C. After dispersion, the graphene solution is 0.3 mg / mL. Take 15 mL of the aqueous solution of LM ultrasonicated and 12 mL of the aqueous solution formed by GO. The mass ratio of LM to GO is 6:2. Add 10 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, adjust the pH to 2, and react at room temperature for 3 h under magnetic stirring. After the reaction, the measured pH is 4, which proves the smooth progress of the reduction, and LM@G is obtained; Take 200 mg of glycine and add 200 mL of water. Add LM@G to the above aqueous solution and react for 2 h. Centrifuge and collect, wash with ethanol and then dry to obtain the noble metal-stably loaded multi-layer hollow sphere LM@G-Pt catalyst.

[0045] Implementation Case 8: Weigh 0.1 g of EGaIn. After melting it into a liquid state, put it into a centrifuge tube and disperse it in 50 mL of ethanol solution. The ultrasonic power is 600 w, the ultrasonic time is 2 h, and the temperature is controlled at 5 °C. After the reaction, it is a uniform solution for standby; Weigh 2.5 mg of GO, add 15 mL of DI water and perform ultrasonic crushing for 1 h. The power is 600 w, and the temperature is controlled at 5 °C. After dispersion, the graphene solution is 0.3 mg / mL. Take 15 mL of the aqueous solution of LM ultrasonicated and 15 mL of the aqueous solution formed by GO. The mass ratio of LM to GO is 6:2. Add 10 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, adjust the pH to 2, and react at room temperature for 3 h under magnetic stirring. After the reaction, the measured pH is 4, which proves the smooth progress of the reduction, and LM@G is obtained; Take 200 mg of glycine and add 200 mL of water. Add LM@G to the above aqueous solution and react for 2 h. Centrifuge and collect, wash with ethanol and then dry to obtain the noble metal-stably loaded multi-layer hollow sphere LM@G-Pt catalyst.

[0046] Implementation Case 9: Weigh 0.1 g of EGaInSn, melt it into a liquid state, put it into a centrifuge tube, add 50 mL of ethanol solution, and then disperse it. The ultrasonic power is 600 w, the ultrasonic time is 2 h, and the ultrasonic temperature is 5 °C. After the reaction, it is a homogeneous solution for standby; Weigh 2.5 mg of GO, add 15 mL of DI water, and perform ultrasonic fragmentation for 1 h. The power is 600 w, and the temperature is controlled at 5 °C. After dispersion, the graphene solution is 0.3 mg / mL. Take 15 mL of the aqueous solution of LM after ultrasonic treatment and 12 mL of the aqueous solution of GO formed. The mass ratio of LM to GO is 6:2. Add 10 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, adjust the pH to 2, and react at room temperature for 3 h under magnetic stirring. After the reaction, the measured pH is 4, which proves the smooth progress of the reduction, and LM@G is obtained; Take 200 mg of glycine and add 200 mL of water. Add LM@G to the above aqueous solution and react for 2 h. Centrifuge and collect, wash with ethanol and then dry to obtain the noble metal-stabilized multi-layer hollow sphere LM@G-Pt catalyst.

Claims

1. A noble metal-loaded multi-layer hollow microsphere liquid metal-based catalyst, characterized in that: By introducing a cationic surfactant on the surface of gallium-based liquid metal (LM), an intermediate configuration is formed in which LM directly bonds with the cationic surfactant and then reacts with metal anions (LM-S + +M - ), or LM is coated with reduced graphene oxide on the surface, then bonds with the cationic surfactant and reacts with metal anions (LM@G-S + +M - ). Furthermore, an electrocatalyst of the LM@M or LM@G-M type with a stable structural support and uniform noble metal loading is obtained. This catalyst has a multi-element hollow structure. The multi-layer structures of LM@M and LM@G-M are, from the inside to the outside, LM, the cationic surfactant, the metal represented by M, and LM, reduced graphene oxide, the cationic surfactant, the metal represented by M. Among them, LM is consumed during the process of reducing graphene oxide and metal ions to form a hollow, while the surfactant, reduced graphene oxide, and M grown on its surface form a multi-layer structure. Among them, S + is the cationic surfactant, M is a certain metal, M - is the ion of this metal, and G is reduced graphene oxide.

2. The liquid metal-based catalyst of a noble metal-loaded multi-layer hollow microsphere according to claim 1, wherein Based on LM-S + +M - The LM@M electrocatalyst obtained from the intermediate configuration has stable multi-layered hollow microspheres with noble metal loading. The noble metal is evenly distributed on its surface, and it has a multi-layered hollow structure. The specific surface area of its hollow structure is 50-200 m 2 / g. The outermost layer of the multi-layered hollow microspheres has a size of 100-300 nm, and the noble metal elements are evenly distributed.

3. The liquid metal-based catalyst of a noble metal-loaded multi-layer hollow microsphere according to claim 1, wherein Based on LM@G-S + +M - The reduced graphene oxide coating for electrocatalytic LM@G-M configuration and the formation of a stable noble metal-loaded multi-layer hollow microsphere structure obtained from the intermediate configuration. The noble metal can be stably and uniformly loaded on Ga and Ga-based liquid metals wrapped by reduced graphene oxide, maintaining long-term stability and electrochemical corrosion resistance. The size of the noble metal layer is 100~300 nm, and the specific surface area of the hollow structure is 50~200m 2 / g.

4. A noble metal-loaded multi-layer hollow microsphere liquid metal-based catalyst according to claim 1, wherein, LM-S + +M in S + That is, the cationic surfactants include: cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), or cetylpyridinium chloride (CPC) that are hydrogen-bonded to LM; sodium dodecyl sulfate (SDS) or n-dodecanethiol (C12) that are sulfur-atom-bonded to liquid metal; LM@G-S + +M - The intermediate configuration uses cationic surfactants that can complex with the positive and negative charges of reduced graphene oxide: poly(diallyldimethylammonium bromide) (PDDA), glutamic acid, or glycine.

5. A noble metal-loaded multi-layered hollow microsphere liquid metal-based catalyst according to claim 1, characterized in that LM-S + +M - or LM@G-S + +M - M in the configurational intermediate - The substances are K2PtCl6, AuCl3HCl4H2O, and Na2PdCl4.

6. The preparation method of a noble metal-loaded multi-layer hollow microsphere liquid metal-based catalyst according to any one of claims 1-5 is prepared by the following steps: Prepare LM@M: Step 1: Configuration of surfactant solution: Select a cationic surfactant and configure it into a solution with a concentration of 1-5 mg / mL. Step 2: Pretreatment of LM: Weigh 0.1 - 0.5 g of LM, melt it into a liquid state in a water bath, and then add 1 - 5 mL of the solution prepared in Step 1 for dispersion. Select an ultrasonic power of 100 - 800 w, control the temperature at 0 - 10 °C, and the ultrasonic time is 1 h. The obtained product is denoted as LM-S + , and perform freeze-drying; Step 3: Preparation of LM@Pt: Weigh 0.1 - 0.5 g of dried LM-S + and react with 2.5 - 10 mL of an aqueous solution of the precious metal salt as described in claim 5 with a concentration of 0.02 mol / L at 25 - 50 °C for 2 h to obtain LM-S + + M - type LM@M electrocatalyst; Prepare LM@G-M Step 1: Dispersion of graphene oxide (GO): Weigh 1-5 mg of GO and 10-20 mL of DI water for ultrasonic fragmentation, disperse for 0.5-4 h under the condition of 100-800 w, control the temperature at 0-10 °C, and obtain a graphene solution with a concentration of 0.1-0.4 mg / mL; Step 2: Preparation of LM@G: LM reduces GO (graphene oxide) to LM@G through an electroreplacement reaction. Calculate the mass of the graphene oxide solution to be 2 - 4 mg according to the solid-liquid ratio in Step 1. Calculate the mass ratio of LM to GO to be 6:3 - 6:1 according to its solid-liquid ratio, and mix them in this proportion. Add 2 - 5 mL of 1 mol / L hydrochloric acid solution to the above LM and GO solutions, and adjust the pH of the mixed solution to 1 - 3. One is to prevent the formation of a dense oxide film on the surface of liquid metal particles, and the other is to provide H for the reduction of GO + Ensure; at room temperature, stir the reaction magnetically for 3 h, wash with water and dry to obtain LM@G; Step 3: Configuration of cationic surfactant: Select a cationic surfactant and configure it into an aqueous solution of 1-4 mg / mL; Step 4: LM@G-S + Preparation: LM@G and a cationic surfactant are mixed at a volume ratio of 1:1 to 1:4 and reacted for 2 h; centrifuged and collected, and after drying, LM@G-S is obtained + ; Step 5: Preparation of LM@G-M: Using LM@G-S + as a support template and sacrificial agent, reacting with 5 - 10 mL of an aqueous solution of the precious metal salt described in claim 5 with a concentration of 0.02 mol / L to obtain LM@G-S + + M - type LM@G-M electrocatalyst.

7. The preparation method of a noble metal-loaded multi-layer hollow sphere liquid metal-based catalyst according to claim 6, characterized in that, During the synthesis of LM@M or LM@G-M, when synthesizing LM particles, the ultrasonic fragmentation power is 100-800 W and the temperature is 0-5 °C.

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