Catalyst rich in Pt-C bonds and preparation and application thereof

Abstract

The invention relates to the technical field of hydrogen production through water electrolysis, in particular to a catalyst rich in Pt-C bonds and preparation and application thereof. The preparation method comprises the following steps: firstly, impregnating a Pt-containing raw material on a carbon material, and performing post-treatment to obtain a Pt-C precursor; and grinding the obtained Pt-C precursor, placing the ground Pt-C precursor in a water vapor atmosphere, and carrying out low-temperature reduction treatment by using plasma generated by inert gas to obtain the catalyst rich in Pt-C bonds. The method provided by the invention is simple, low in treatment temperature, high in treatment speed, high in electron energy, simple in steps, safe and reliable, and does not use toxic reagents; the prepared catalyst rich in Pt-C bonds can be applied to electro-catalytic hydrogen production in a full pH range, and is far better than an existing commercial platinum catalyst.

Description

Technical Field

[0001] This invention relates to the field of water electrolysis for hydrogen production, and in particular to a catalyst rich in Pt-C bonds and its preparation and application. Background Technology

[0002] Hydrogen energy, as a highly promising new energy source, is a crucial component of the future energy system due to its cleanliness and renewability. Water electrolysis for hydrogen production, a key method, hinges on the development of efficient and stable electrocatalysts. Platinum nanoparticles, with their excellent catalytic performance, have demonstrated significant application potential in water electrolysis for hydrogen production and are considered one of the best hydrogen evolution electrocatalysts currently available. However, despite their superior performance, platinum nanoparticles still face several challenges in practical applications, especially in large-scale industrial applications. First, commercial platinum-carbon (Pt / C) catalysts generally contain high platinum contents, such as 20 wt% and 40 wt%. This high platinum content not only increases production costs but may also lead to low catalyst utilization in practical applications, thus limiting their economic benefits. Therefore, reducing the platinum content while maintaining catalytic performance and improving the catalyst's cost-effectiveness is a key research direction. Second, the hydrogen production efficiency of platinum nanoparticles in alkaline and neutral electrolytes is relatively low. This is mainly because the number of catalytically active sites on platinum nanoparticles is limited in these two electrolytes, resulting in a restricted reaction rate. To improve hydrogen production efficiency, new catalyst structures or modification methods need to be developed to increase the number of active sites or enhance their catalytic activity. Furthermore, the lifespan of platinum nanoparticles is also a key factor limiting their large-scale industrial application. In practical applications, the catalytic performance of platinum nanoparticles gradually declines due to electrolyte corrosion, catalyst agglomeration, and detachment, leading to a shortened lifespan. Therefore, improving the stability and durability of platinum nanoparticles and extending their lifespan is another important research direction.

[0003] Currently, academic and industrial communities are actively conducting research to address key issues with platinum catalysts, such as high platinum loading, low active site utilization efficiency, difficulty in large-scale production, and limited lifespan. For example, patent CN114855180A proposes a strategy for preparing a low-platinum-loading hydrogen evolution electrocatalyst based on polyacid derivatives. However, this strategy involves complex and costly chemical reagents such as dopamine hydrochloride, ammonia, and tris(hydroxymethyl)aminomethane hydrochloride, and requires Pt to be processed at high temperatures ranging from 700 to 900°C. 4+The reduction step undoubtedly increases the complexity and energy consumption of the preparation process, while also posing safety hazards. On the other hand, patent CN114134532A developed a platinum single-atom hydrogen evolution electrocatalyst and its preparation process, which exhibited excellent activity and stability. However, its preparation process unfortunately uses dimethylimidazole and methanol, two substances classified as Group 2B carcinogens by the World Health Organization, which contradicts the principles of green chemistry and sustainable development. Furthermore, the high carbonization temperature requirement of 800°C to 1100°C greatly limits the widespread application of this technology in industrial production. However, both of the above methods rely on strong reducing agents such as sodium borohydride or hydrogen to complete the Pt process. 4+ The restoration process.

[0004] Therefore, it is crucial to provide a method for preparing platinum catalysts that can simplify the preparation process and reduce energy consumption and safety hazards. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a catalyst rich in Pt-C bonds, its preparation, and its application. This invention innovatively employs plasma technology to directly generate highly reducing hydrated hydrogen ions through a discharge process, thereby achieving the desired Pt-C bond concentration. 4+ Effective reduction at lower temperatures; this method has the advantages of using green raw materials, simple process, low operating temperature and low energy consumption, making it suitable for large-scale industrial applications.

[0006] The objective of this invention can be achieved through the following technical solutions: The first objective of this invention is to provide a method for preparing a catalyst rich in Pt-C bonds, comprising the following steps: (S1) Pt-containing raw materials are impregnated onto carbon materials, and after post-treatment, Pt-C precursors are obtained; (S2) The Pt-C precursor obtained in step (S1) is ground and placed in a water vapor atmosphere. Low-temperature discharge treatment (low-temperature plasma reduction) is performed using plasma generated by inert gas to obtain a catalyst rich in Pt-C bonds (with ultra-small Pt nanoparticles and abundant Pt-C bonds; when applied, it can enhance the interaction between the catalyst and the support, provide a large number of reactive sites, and promote the rapid progress of electrochemical reactions).

[0007] In one embodiment of the present invention, in step (S1), the Pt-C-containing raw material is selected from one of Pt salts or Pt compounds; The Pt salt is selected from one or more of chloroplatinate, platinum acetylacetonate, platinum chloride, or potassium chloroplatinate. The Pt compound is selected from one of PtO, PtO2, PtS, PtS2, PtBr2, PtF2, H2PtCl6 and their ammonium salts; The carbon material is selected from one or more of carbon nanotubes, carbon fibers, carbon spheres, or graphene.

[0008] In one embodiment of the present invention, in step (S1), the mass ratio of Pt-containing raw material to carbon material is 0.002~0.05:1.

[0009] In one embodiment of the present invention, in step (S1), the post-processing is to allow the mixture to stand at room temperature and then perform a drying process (preferably, a forced-air drying process).

[0010] In one embodiment of the present invention, the settling time is 8 to 24 hours. During the drying process, the temperature is 110~150 ℃ and the time is 8~24 h.

[0011] In one embodiment of the present invention, in step (S2), the concentration of water vapor in the water vapor atmosphere is 15-35%; The inert gas is selected from either argon or nitrogen.

[0012] In one embodiment of the present invention, in step (S2), the plasma is selected from one of corona discharge plasma, arc discharge plasma, dielectric barrier discharge plasma or glow discharge plasma.

[0013] In one embodiment of the present invention, in step (S2), during the low-temperature discharge process, the macroscopic temperature range is 20~35 ℃, the gas flow rate is 10~200 sccm, the discharge power range is 1~300 W, and the time is 1~70 min.

[0014] The method provided by this invention is simple, has a low processing temperature, a fast processing speed, high electron energy, simple steps, is safe and reliable, and does not use toxic reagents. It not only simplifies the preparation process and reduces energy consumption and safety hazards, but also has the potential to open up new avenues for the green, efficient, and large-scale production of platinum catalysts.

[0015] A second objective of this invention is to provide a catalyst rich in Pt-C bonds, which is prepared by the above method.

[0016] The third objective of this invention is to provide an application of a catalyst rich in Pt-C bonds in electrocatalytic hydrogen production, wherein the pH during the electrocatalytic hydrogen production process is 0-14.

[0017] The catalyst rich in Pt-C bonds provided by this invention (low Pt content, small and uniformly dispersed Pt particles, rich in Pt-C bonds, excellent hydrogen evolution performance in electrolytes of all pH, and excellent quality activity) can be applied to electrocatalytic hydrogen production in the full pH range, which is far superior to existing commercial platinum catalysts.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) The catalyst rich in Pt-C bonds in this invention has more active sites and higher hydrophilicity, which effectively reduces the actual potential during the electrolysis process; (2) The catalyst rich in Pt-C bonds in this invention can effectively reduce the energy barrier of the reaction, shorten the electron transfer path, improve the electron transfer efficiency, and have long-term stability. (3) The catalyst rich in Pt-C bonds in this invention exhibits excellent hydrogen production performance in acidic, alkaline and neutral electrolytes; (4) The preparation process of the catalyst rich in Pt-C bonds in this invention is simple, safe, controllable, low temperature, green and inexpensive. Attached Figure Description

[0019] Figure 1 XPS image of the electrocatalyst prepared in Example 1; Figure 2 XPS image of the electrocatalyst prepared in Example 2; Figure 3 XPS image of the electrocatalyst prepared in Example 3; Figure 4 XPS image of the electrocatalyst prepared in Example 4; Figure 5 This is a schematic diagram showing the particle size of the electrocatalyst prepared in Example 4; Figure 6 This is a stability test graph of the electrocatalyst prepared in Example 4; Figure 7 XPS image of the electrocatalyst prepared in Example 5; Figure 8 The electrocatalysts prepared in Examples 6-8 were used at a current density of 10 mA cm⁻¹. -2 A graph showing the combination of overpotential and mass activity at a potential of 100 mV; Figure 9 The electrocatalysts prepared in Comparative Examples 1-2 and Example 4 had a current density of 10 mA cm⁻¹. -2 Overpotential at that time. Detailed Implementation

[0020] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0021] Unless otherwise specified, all reagents used in the following embodiments are commercially available reagents, and all detection methods and techniques used are conventional detection methods and techniques in the art.

[0022] Example 1 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was evenly spread in a 10 cm diameter glass petri dish, and 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere). The mixture was stirred until homogeneous. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow discharge plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). Its XPS image is shown below. Figure 1 As shown; During the low-temperature discharge process, each discharge lasted 3 minutes, was performed once, the chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W.

[0023] Example 2 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was evenly spread in a 10 cm diameter glass petri dish, and 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere). The mixture was stirred until homogeneous. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow discharge plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). Its XPS image is shown below. Figure 2 As shown; During the low-temperature discharge process, each discharge lasted 3 minutes, with 5 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was dispersed, and 1 mL of deionized water was added and stirred until homogeneous.

[0024] Example 3 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was evenly spread in a 10 cm diameter glass petri dish, and 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere). The mixture was stirred until homogeneous. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow discharge plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). Its XPS image is shown below. Figure 3 As shown; During the low-temperature discharge process, each discharge lasted 3 minutes, with 10 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0025] Example 4 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was evenly spread in a 10 cm diameter glass petri dish, and 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere). The mixture was stirred until homogeneous. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow discharge plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). Its XPS image is shown below. Figure 4 As shown, the particle size is as follows Figure 5 As shown, the stability is as follows Figure 6 As shown; During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0026] Example 5 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was evenly spread in a 10 cm diameter glass petri dish, and 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere). The mixture was stirred until homogeneous. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow discharge plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). Its XPS image is shown below. Figure 7 As shown; During the low-temperature discharge process, each discharge lasted 3 minutes, with 20 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was dispersed, and 1 mL of deionized water was added and stirred until homogeneous.

[0027] The Pt-C bond-rich catalysts prepared in Examples 1-5 were structurally characterized, and the results are as follows: Figures 1-4 as well as Figure 7 As shown.

[0028] pass Figures 1-4 as well as Figure 7 It can be observed that the valence state of the sample changes with the number of discharges. Specifically, Pt... 4+ and Pt 0+ The content of Pt gradually decreases with increasing discharge cycles, while the content of Pt... 0+ The content of Pt gradually increased. This indicates that the low-temperature plasma technology successfully reduced Pt, and that the valence state of Pt can be effectively controlled by changing the discharge parameters. 0+ and Pt δ+ The peak gradually shifted towards higher binding energies as the processing time increased, indicating the formation of Pt-C bonds.

[0029] The catalysts prepared in Examples 1-5 can be further used in electrocatalytic hydrogen production. Electrocatalytic hydrogen production of the catalysts was studied using a three-electrode system from Shanghai Chenhua Company. The results are shown in Table 1. Table 1 shows that the novel catalysts rich in Pt-C bonds exhibit significantly better catalytic performance than commercial platinum carbon hydrogen evolution catalysts, specifically in terms of low overpotential and high mass activity.

[0030] Table 1. Electrocatalysts prepared in Examples 1-5 at a current density of 10 mA cm⁻¹ -2 Summary table of overpotential and mass activity at a potential of 100 mV In Table 1, the acidic electrolyte was a 0.5 M H2SO4 solution with pH 0; the neutral electrolyte was a 1.0 M PBS solution with pH 7; the alkaline electrolyte was a 1.0 M KOH solution with pH 14; and the 20% Pt / C was purchased from Anhui Zesheng Technology Co., Ltd. (E063567).

[0031] Example 6 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 6.7 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance, and seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0032] Example 7 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 22.3 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance, and seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0033] Example 8 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 27.1 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance, and seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 200 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0034] The novel catalysts rich in Pt-C bonds prepared in Examples 6-8 were subjected to performance testing, such as... Figure 8 As shown. (Through) Figure 8 It can be found that the catalytic performance of catalysts rich in Pt-C bonds can be controlled by adjusting the Pt content, specifically in terms of low overpotential and high mass activity.

[0035] Example 9 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 100 W. After each discharge, the glass petri dish was removed, the sample was dispersed, and 1 mL of deionized water was added and stirred until homogeneous.

[0036] Example 10 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 150 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0037] Example 11 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 250 W. After each discharge, the glass petri dish was removed, the sample was stirred, and 1 mL of deionized water was added and stirred until homogeneous.

[0038] Example 12 This embodiment provides a method for preparing a catalyst rich in Pt-C bonds, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was spread evenly in a glass petri dish with a diameter of 10 cm, 1 mL of deionized water was added (the addition of deionized water provides a water vapor atmosphere), and the mixture was stirred evenly. Then, the glass petri dish containing the Pt-C precursor powder was placed in the chamber of a glow plasma and subjected to low-temperature discharge treatment under an Ar atmosphere to obtain a catalyst rich in Pt-C bonds (a multivalent platinum nanoparticle composite electrocatalyst supported on carbon nanotubes). During the low-temperature discharge process, each discharge lasted 3 minutes, with 15 discharge cycles. The chamber vacuum was 80 Pa, the gas flow rate was 150 sccm, and the discharge power was 300 W. After each discharge, the glass petri dish was removed, the sample was dispersed, and 1 mL of deionized water was added and stirred until homogeneous.

[0039] Comparative Example 1 This comparative example provides a method for preparing Pt / CNT-H materials, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was placed in a 10 cm long boat crucible and calcined at 350 °C for 2 h in a 5% H2 / Ar mixed atmosphere to obtain Pt / CNT-H material.

[0040] Comparative Example 2 This comparative example provides a method for preparing Pt / CNT-B material, as detailed below: (S1) Place 13.4 mg H2PtCl6·6H2O and 500 mg carbon nanotubes in a 50 mL beaker, then add 2 mL of deionized water, and stir thoroughly with a glass rod for 1 h to obtain a uniform mud-like substance. Seal the mouth of the beaker with a sealing film. The small beaker was placed at room temperature for 12 h, and then dried in a forced-air drying oven at 110 ℃ for 12 h to obtain the Pt-C precursor. (S2) The Pt-C precursor obtained in step (S1) is ground to obtain Pt-C precursor powder with a particle size of 50~150 µm; 200 mg of Pt-C precursor powder was placed in a 50 mL round-bottom flask, and then 10 mg of NaBH4 was added to the flask and stirred magnetically for 2 h to obtain Pt / CNT-B material.

[0041] The catalytic performance of Comparative Examples 1-2 and Example 4 will be compared. Figure 9 )pass Figure 9 It can be observed that the Pt-C material prepared by plasma treatment exhibits far superior electrocatalytic HER performance compared to Pt / CNT-H and Pt / CNT-B.

[0042] In summary, compared with traditional Pt / C material preparation methods, the plasma technology proposed in this invention can achieve green synthesis of Pt / C materials under conditions without hydrogen and strong reducing substances, and has superior catalytic performance.

[0043] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the interpretation of the present invention, without departing from the scope of the invention, should be within the protection scope of the present invention.

Claims

1. A method for preparing a catalyst rich in Pt-C bonds, characterized in that, Includes the following steps: (S1) Pt-containing raw materials are impregnated onto carbon materials, and after post-treatment, Pt-C precursors are obtained; (S2) The Pt-C precursor obtained in step (S1) is ground and placed in a water vapor atmosphere. Low-temperature discharge treatment is performed using plasma generated by inert gas to obtain a catalyst rich in Pt-C bonds.

2. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S1), the Pt-C-containing raw material is selected from one of Pt salts or Pt compounds; The Pt salt is selected from one or more of chloroplatinate, platinum acetylacetonate, platinum chloride, or potassium chloroplatinate. The Pt compound is selected from one of PtO, PtO2, PtS, PtS2, PtBr2 or PtF2; The carbon material is selected from one or more of carbon nanotubes, carbon fibers, carbon spheres, or graphene.

3. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S1), the mass ratio of Pt-containing raw material to carbon material is 0.002~0.05:

1.

4. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S1), the post-processing is to allow the mixture to stand at room temperature and then dry it.

5. The method for preparing a catalyst rich in Pt-C bonds according to claim 4, characterized in that, During the settling process, the settling time is 8~24 hours; During the drying process, the temperature is 110~150 ℃ and the time is 8~24 h.

6. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S2), the concentration of water vapor in the water vapor atmosphere is 15-35%; The inert gas is selected from either argon or nitrogen.

7. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S2), the plasma is selected from one of corona discharge plasma, arc discharge plasma, dielectric barrier discharge plasma, or glow discharge plasma.

8. The method for preparing a catalyst rich in Pt-C bonds according to claim 1, characterized in that, In step (S2), during the low-temperature discharge process, the macroscopic temperature range is 20~35 ℃, the gas flow rate is 10~200 sccm, the discharge power range is 1~300 W, and the time is 1~70 min.

9. A catalyst rich in Pt-C bonds, characterized in that, It is prepared by any of the methods described in claims 1 to 8.

10. The application of the Pt-C bond-rich catalyst as described in claim 9 in electrocatalytic hydrogen production, characterized in that, During electrocatalytic hydrogen production, the pH ranges from 0 to 14.

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