A Ni3Ga 0.8 Pt 0.2 / CC catalysts, their preparation methods, and applications

Abstract

This invention belongs to the field of electrocatalysis technology, specifically relating to a Ni3Ga 0.8 Pt 0.2 / CC catalysts, their preparation methods and applications, including carbon cloth and Ni3Ga supported on carbon cloth. 0.8 Pt 0.2 Catalyst. This invention achieves the loading of three metal sites on carbon cloth via impregnation, and finally obtains Ni3Ga by reduction with a 10% hydrogen-nitrogen mixed gas. 0.8 Pt 0.2 / CC catalyst, as demonstrated in experiments, Ni3Ga 0.8 Pt 0.2 / CC catalysts can efficiently electrolyze simulated seawater and exhibit high HER catalytic activity in alkaline environments.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysis technology, specifically relating to a Ni3Ga 0.8 Pt 0.2 / CC catalysts, their preparation methods, and applications. Background Technology

[0002] In the field of renewable energy, hydrogen energy has attracted attention due to its high efficiency and environmental friendliness. Hydrogen energy refers to a clean energy form that uses hydrogen gas as an energy carrier, and the production of hydrogen gas is closely related to the development of hydrogen energy. To date, water electrolysis is considered a clean and sustainable method for producing hydrogen. However, traditional water electrolysis methods suffer from low efficiency and high cost; therefore, developing efficient catalysts is crucial to improving the efficiency of the water electrolysis hydrogen production reaction.

[0003] By designing and optimizing catalyst structures, catalytic activity and stability can be improved, thereby reducing energy consumption and costs. Platinum (Pt) is one of the most commonly used HER catalysts, exhibiting high catalytic activity and stability. However, its scarcity and high cost limit its development in large-scale applications.

[0004] In recent years, with the gradual maturation of binary alloy electrocatalyst technology, current research has shifted from the preparation of binary alloy electrocatalysts to the study of more complex ternary alloy systems. Ternary alloys exhibit superior electrocatalytic performance compared to binary alloys, attributed to the synergistic effect among all three elements, forming more diverse active sites. These sites have stronger adsorption and activation capabilities for specific reactions, thereby improving catalytic efficiency. Simultaneously, ternary alloys offer flexibility in adjusting catalytic performance. By changing the proportions of each metal element in the alloy, the electronic structure of the catalyst can be optimized. The multiple metal elements in ternary alloys can adjust the electron distribution on the catalyst surface, forming a more favorable electronic structure, promoting electron transfer and reactant adsorption, thereby improving the selectivity and activity of the catalytic reaction. However, although existing ternary alloy catalysts can reduce the overpotential of the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER), their activity still cannot compare with pure noble metal catalysts (such as Pt or Ir-based catalysts). Furthermore, in acidic or alkaline electrolytes, the non-noble metals (such as Ni and Co) in ternary alloys are prone to dissolution or oxidation, leading to catalyst inactivation.

[0005] Therefore, developing efficient, low-cost, and highly stable ternary alloy catalysts is crucial for improving the efficiency of hydrogen desorption from water. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the purpose of this invention is to provide a Ni3Ga 0.8 Pt 0.2 / CC catalyst, its preparation method and application: Metal salt loading on carbon cloth is achieved via wet impregnation, and Ni3Ga is obtained by thermal decomposition in a 10% hydrogen-nitrogen mixture. 0.8 Pt 0.2 The / CC catalyst, which can efficiently electrolyze simulated seawater, demonstrates that preparing multi-element alloy catalysts by doping with suitable metal elements is an effective strategy for preparing high-performance electrocatalysts.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] In a first aspect, the present invention provides a Ni3Ga 0.8 Pt 0.2 / CC catalyst, including carbon cloth and Ni3Ga supported on carbon cloth. 0.8 Pt 0.2 catalyst.

[0009] In some other embodiments, the Ni3Ga 0.8 Pt 0.2 / CC catalyst Ni3Ga 0.8 Pt 0.2 The catalyst loading is 55-60 wt%, of which the loadings of Ni, Ga and Pt are 30-40 wt%, 10-15 wt% and 10-15 wt%, respectively.

[0010] The Ni3Ga 0.8 Pt 0.2 The particle size of the / CC catalyst is 150-250 nm;

[0011] Preferably, the Ni3Ga 0.8 Pt 0.2 / CC catalyst Ni3Ga 0.8 Pt 0.2 The catalyst loading was 57 wt%, of which the loadings of Ni, Ga and Pt were 35 wt%, 12 wt% and 10 wt%, respectively.

[0012] The Ni3Ga 0.8 Pt 0.2 The / CC catalyst has a particle size of 200 nm.

[0013] Secondly, the present invention provides the Ni3Ga described in the first aspect. 0.8 Pt 0.2 The preparation method of / CC catalyst includes the following steps:

[0014] (1) Mix carbon cloth, nickel source, gallium source and platinum source and then soak them in water to obtain a mixture;

[0015] (2) The mixture was dried and reduced to obtain Ni3Ga 0.8 Pt 0.2 / CC catalyst.

[0016] In some other implementations, in step (1),

[0017] The molar ratio of the nickel source, gallium source, and platinum source is (2.5-3.0):(0.7-0.9):(0.1-0.3);

[0018] The impregnation process involves ultrasonic dispersion for 10-30 minutes and impregnation for 10-15 hours.

[0019] Preferably, the molar ratio of the nickel source, gallium source, and platinum source is 3.0:0.8:0.2;

[0020] The impregnation process involves ultrasonic dispersion for 20 minutes and impregnation for 12 hours.

[0021] In some other embodiments, the carbon cloth is pretreated before mixing. The pretreatment method is to soak the carbon cloth in a mixed solution of acetone and ethanol, vacuum dry it, then put it into a sulfuric acid solution, wash it with water until neutral, and finally vacuum dry it to obtain the final product.

[0022] Preferably, the pretreatment method is as follows: the soaking temperature is 25-30℃, the volume ratio of acetone to ethanol is 1:(1-3), the vacuum drying temperature is 55-60℃, the vacuum drying time is 10-12h, and the sulfuric acid solution is a solution of sulfuric acid and water with a volume ratio of 1:(1-2).

[0023] In some other embodiments, in step (1), the nickel source is one or more of nickel nitrate, nickel chloride, and nickel sulfate;

[0024] The gallium source is one or more of gallium nitrate, gallium chloride, and gallium sulfate;

[0025] The platinum source is one or more of chloroplatinic acid, lithium chloroplatinate, and platinum acetylacetonate.

[0026] In some other embodiments, in step (2), the drying temperature is 80-120°C and the time is 10-15 hours;

[0027] The reduction is carried out at a temperature of 600-800℃ for 1-5 hours in a hydrogen-nitrogen mixture.

[0028] Preferably, the reduction temperature is 700°C, the time is 2 hours, and the hydrogen-nitrogen mixture is a hydrogen-nitrogen mixture with a volume ratio of 10%.

[0029] Thirdly, the present invention provides the Ni3Ga described in the first aspect. 0.8Pt 0.2 Application of / CC catalyst in hydrogen production by water electrolysis.

[0030] In some other embodiments, the water is simulated seawater; preferably, the simulated seawater is water containing 1M KOH and 0.1M NaCl.

[0031] Fourthly, the present invention provides a method for producing hydrogen by electrolysis of water, using the Ni3Ga described in the first aspect. 0.8 Pt 0.2 / CC catalyst was used as a catalyst for hydrogen production by water electrolysis in a 1M KOH environment.

[0032] The beneficial effects are as follows:

[0033] This invention synthesizes a novel alloy catalyst Ni3Ga using a surface functionalization deposition method and a hydrogen reduction method. 0.8 Pt 0.2 / CC, capable of efficiently electrolyzing simulated seawater, exhibits excellent electrochemical performance in alkaline environments, and the catalyst operates at -10 mA cm⁻¹. -2 The LSV overpotential was 26 mV, which is superior to the performance of most catalysts. EXAFS and XPS characterizations showed that electron transfer occurred among the three metals, and electronic perturbation occurred between the Pt sites and the carbon cloth support. This charge redistribution directly accelerated the water adsorption behavior at Ni and Pt sites during catalysis, thereby promoting the electrochemical reaction. Through electron transfer between Ni and Ga, more electrons were transferred to Ga. The high-valence Ni reduced the hydrogen adsorption rate and lowered the binding energy of the reaction intermediates, thus accelerating the hydrogen evolution reaction (HER) process of the electrocatalyst. Attached Figure Description

[0034] Figure 1 The image shows a scanning electron microscope (SEM) image of the catalyst prepared in Example 1, where (a) is a magnified view of (b).

[0035] Figure 2 The image shown is a transmission electron microscope (TEM) image of the catalyst prepared in Example 1, where (b) is a magnified view of (a).

[0036] Figure 3 XRD patterns of the catalysts prepared in Example 1 and Comparative Examples 1 and 2;

[0037] Figure 4 XPS images of the catalyst prepared in Example 1, including (a) Ni 2p, (b) Ga 2p and (c) Pt 4f.

[0038] Figure 5 (a) EXAFS spectra and (b) Fourier transforms of the catalysts prepared in Example 1 and Comparative Examples 2, 3, and 5;

[0039] Figure 6 EXAFS wavelet transform analysis of the platinum foils (a) and (b) of the catalyst prepared in Example 1;

[0040] Figure 7 HER LSV curves of the catalysts prepared in Example 1 and Comparative Examples 2-5 under alkaline conditions of 1M KOH;

[0041] Figure 8 The HER LSV curves of the catalysts prepared in Example 1 and Comparative Example 5 under alkaline simulated seawater conditions are shown in the graphs.

[0042] Figure 9 HER LSV curves of the catalysts prepared in Example 1 and Comparative Examples 6-7 under alkaline conditions of 1M KOH;

[0043] Figure 10 The HER LSV curves of the catalysts prepared in Example 1 and Comparative Examples 8-9 under an alkaline environment of 1M KOH are shown.

[0044] Figure 11 The HER LSV curves of the catalysts prepared in Example 1 and Comparative Example 10 under an alkaline environment of 1M KOH are shown. Detailed Implementation

[0045] The overall inventive concept of this invention is to improve catalytic activity and stability by designing and optimizing the catalyst structure, thereby reducing energy consumption and costs. Platinum (Pt) is one of the most commonly used HER catalysts, possessing high catalytic activity and stability. However, its scarcity and high cost limit its development in large-scale applications. Therefore, this invention researches and develops platinum alloy catalysts. In the alloy catalyst, the interaction between different metal cations allows one metal to regulate the electron distribution of another metal ion through its electron-donating or accepting ability, resulting in a ligand effect. This, in turn, affects the properties and catalytic performance of the catalytic active sites, thereby improving hydrogen production efficiency. Carbon cloth (CC), as an electrocatalyst support, has shown many advantages in the field of electrochemistry, especially when used as a support material to support active catalysts. As a support, carbon cloth possesses excellent high conductivity, high surface area, mechanical strength, and stability. Therefore, during catalyst preparation, its high specific area and stability as a support allow catalyst particles to be uniformly and stably deposited on the catalyst surface without affecting the catalytic reaction.

[0046] This invention utilizes surface functional deposition to prepare Ni3Ga on 1*2 cm carbon cloth. 0.8 Pt 0.2 / CC catalyst, which is prepared by reduction of a 10% hydrogen-nitrogen mixture at 700°C. Although Ni3Ga0.8 Pt 0.2 The / CC catalyst has a low Pt content, but as an electrocatalyst for HER, the ternary alloy Ni3Ga 0.8 Pt 0.2 / CC exhibits extremely high alkaline HER catalytic activity compared to other binary alloys. Its catalytic performance was evaluated by simulating the seawater hydrogen production reaction via electrolysis. The results show that Ni3Ga... 0.8 Pt 0.2 / CC catalysts can efficiently electrolyze simulated seawater. Preparing trimetallic nanocatalysts by doping with suitable metal elements is an effective strategy for developing high-performance electrocatalysts.

[0047] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments and comparative examples.

[0048] The pretreatment method for the carbon cloth is as follows: To reduce the amount of adhesive and oil adhering to the surface of the carbon cloth, it is first soaked in a mixed solution of acetone and ethanol (volume ratio 1:1) at 30°C for 15 minutes, and then dried overnight in a vacuum drying oven at 60°C to remove residual ethanol and acetone. Next, the dried carbon cloth is immersed in a sulfuric acid solution (H2SO4:H2O, volume ratio 1:1) for one hour, followed by washing with deionized water until neutral. Finally, the pretreated carbon cloth is vacuum dried overnight at 60°C.

[0049] I. Catalyst Preparation

[0050] Example 1

[0051] Ni3Ga 0.8 Pt 0.2 The steps for preparing the / CC catalyst using the wet impregnation method are as follows:

[0052] Pretreated carbon cloth was mixed with 0.3771 g nickel nitrate, 0.0664 g gallium nitrate, and 0.0240 g chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.8 / 0.2 and a total metal ion concentration of 1.6 mmol. The metal salts and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was dried in an oven at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0053] Comparative Example 1

[0054] Unlike Example 1, Ni3Ga was prepared without the addition of chloroplatinic acid. 0.8 The specific preparation steps for the / CC catalyst are as follows:

[0055] Pretreated carbon cloth was mixed with 0.3771 g of nickel nitrate and 0.0664 g of gallium nitrate in a 100 mL beaker, with a Ni / Ga molar ratio of 3 / 0.8 and a total metal ion content of 1.55 mmol. The metal salt and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0056] Comparative Example 2

[0057] Unlike Example 1, Ni3Pt was prepared without adding gallium nitrate. 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0058] The pretreated carbon cloth was mixed with 0.3771 g of nickel nitrate and 0.0240 g of chloroplatinic acid in a 100 mL beaker, where the molar ratio of Ni to Pt was 3 / 0.2 and the total metal ion content was 1.35 mmol. The metal salt and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed for 2 hours in a tube furnace at 700 °C under a 10% hydrogen-nitrogen mixed atmosphere.

[0059] Comparative Example 3

[0060] Unlike Example 1, nickel nitrate was not added to prepare Ga. 0.8 Pt 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0061] Pretreated carbon cloth was mixed with 0.0664 g gallium nitrate and 0.0240 g chloroplatinic acid in a 100 mL beaker, with a Ga / Pt molar ratio of 0.8 / 0.2 and a total metal ion content of 0.3 mmol. The metal salt and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed for 2 hours in a tube furnace at 700 °C under a 10% hydrogen-nitrogen mixed atmosphere.

[0062] Comparative Example 4

[0063] Unlike Example 1, Pt was prepared without the addition of nickel nitrate and gallium nitrate. 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0064] The pretreated carbon cloth was mixed with 0.0240 g of chloroplatinic acid and placed in a beaker (100 mL). The metal salt and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After impregnation for 12 hours, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, it was reduced in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0065] Comparative Example 5

[0066] The preparation steps of commercial Pt / C catalysts are as follows:

[0067] Mix 480 μL of anhydrous ethanol solution, 20 μL of Nafion solution and 5 mg of Pt / C sample in a beaker (10 mL), stir thoroughly and sonicate for 30 min. Take 100 μL of the prepared Pt / C sample and coat it evenly on carbon cloth to obtain a commercial Pt / C catalyst.

[0068] Comparative Example 6

[0069] Unlike Example 1, the molar ratio of gallium nitrate was increased from 0.8 to 0.9 to prepare Ni3Ga. 0.9 Pt 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0070] The pretreated carbon cloth was mixed with 0.3493 g of nickel nitrate, 0.0908 g of gallium nitrate, and 0.0201 g of chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.9 / 0.1. The metal salts and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0071] Comparative Example 7

[0072] Unlike Example 1, the molar ratio of gallium nitrate was reduced from 0.8 to 0.7, and the molar ratio of chloroplatinic acid was increased from 0.2 to 0.3 to prepare Ni3Ga. 0.7 Pt 0.3 The specific preparation steps for the / CC catalyst are as follows:

[0073] The pretreated carbon cloth was mixed with 0.3329 g of nickel nitrate, 0.0769 g of gallium nitrate, and 0.0395 g of chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.7 / 0.3. The metal salts and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was placed in an oven and dried at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0074] Comparative Example 8

[0075] Unlike Example 1, the reduction temperature was lowered from 700°C to 600°C while the reduction time remained constant, to prepare Ni3Ga. 0.8 Pt 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0076] Pretreated carbon cloth was mixed with 0.3771 g nickel nitrate, 0.0664 g gallium nitrate, and 0.0240 g chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.8 / 0.2 and a total metal ion concentration of 1.6 mmol. The metal salts and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was dried in an oven at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 600 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0077] Comparative Example 9

[0078] Unlike Example 1, the reduction temperature was increased from 700°C to 800°C, while the reduction time remained constant, to prepare Ni3Ga. 0.8 Pt 0.2 The specific preparation steps for the / CC catalyst are as follows:

[0079] Pretreated carbon cloth was mixed with 0.3771 g nickel nitrate, 0.0664 g gallium nitrate, and 0.0240 g chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.8 / 0.2 and a total metal ion concentration of 1.6 mmol. The metal salts and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was dried in an oven at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 800 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0080] Comparative Example 10

[0081] Unlike Example 1, pretreated nickel foam (NF) was used instead of treated carbon cloth (CC) as the carrier to prepare Ni3Ga. 0.8 Pt 0.2 The specific preparation steps for the / NF catalyst are as follows:

[0082] Pretreated nickel foam was mixed with 0.3771 g nickel nitrate, 0.0664 g gallium nitrate, and 0.0240 g chloroplatinic acid in a 100 mL beaker, with a Ni / Ga / Pt molar ratio of 3 / 0.8 / 0.2 and a total metal ion concentration of 1.6 mmol. The metal salt and carbon cloth were submerged in distilled water, sonicated for 20 minutes, and then impregnated for 12 hours. After 12 hours of impregnation, the solution was dried in an oven at 100 °C for 12 hours until all water was drained. Subsequently, reduction was performed in a tube furnace at 700 °C for 2 hours under a 10% hydrogen-nitrogen mixed atmosphere.

[0083] The pretreatment method for the nickel foam is as follows: the nickel foam is cut to the same size as the carbon cloth in Example 1, immersed in hydrochloric acid solution (10 ml HCl + 50 mL water) and ultrasonically treated for 30 min to remove the oxide layer on its surface. It is then washed with deionized water until neutral and spun dry. Subsequently, it is immersed in acetone / ethanol solution and ultrasonically treated for 10-30 min, and then rinsed with deionized water.

[0084] II. Performance Characterization

[0085] Figure 1 The image shows a scanning electron microscope (SEM) image of the catalyst prepared in Example 1, where (a) is a magnified view of (b). From... Figure 1 It can be seen that Ni3Ga 0.8 Pt 0.2 / CC catalyst has a particle size of 150-200nm, Ni3Ga 0.8 Pt 0.2 / CC catalysis achieved uniform and high-density growth on carbon cloth substrates; the high-density loading effectively improved the exposure of active sites, thereby significantly enhancing its catalytic activity in electrolyte environments, while also making more effective use of the high conductivity and three-dimensional porous structure of carbon cloth substrates, providing an efficient reaction interface for electrocatalytic processes.

[0086] Figure 2 The image shown is a transmission electron microscope (TEM) image of the catalyst prepared in Example 1, where (b) is a magnified view of (a). From... Figure 2 It can be seen that in Ni3Ga 0.8 Pt 0.2In the high-resolution transmission electron microscopy (HRTEM) image of the / CC composite material, two clear lattice fringes with interlayer spacings of 0.206 nm and 0.272 nm can be found, corresponding to the (111) crystal plane of Ni (PDF#04-001-0091) and the (110) crystal plane of Ni3Pt (PDF#01-074-6872), respectively. Compared with the (111) crystal plane of Ni (PDF#04-001-0091), Ni3Ga 0.8 Pt 0.2 The slightly increased interlayer spacing of the (111) crystal plane of Ni in / CC is likely due to the interaction between Pt / Ga and Ni elements. The synergistic effect between different elements can significantly optimize the electronic structure, thereby significantly enhancing the Ni3Ga... 0.8 Pt 0.2 Catalytic activity of / CC in alkaline HER.

[0087] Figure 3 The images show the XRD patterns of the catalysts prepared in Example 1 and Comparative Examples 1 and 2. Figure 3 It can be seen that Ni3Ga 0.8 The diffraction peaks of / CC at 2θ = 44.3°, 51.6°, and 75.9° correspond to the (111), (200), and (220) crystal planes, respectively, which are identical to the standard X-ray diffraction pattern (PDF#04-001-1136) of the Ni face-centered cubic structure. By comparing Ni3Ga... 0.8 Pt 0.2 / CC, Ni3Pt 0.2 / CC and Ni3Ga 0.8 The diffraction peak position of / CC clearly shows Ni3Ga 0.8 Pt 0.2 / CC and Ni3Pt 0.2 The diffraction peak position of Ni in the / CC composite material shifts to a lower 2theta value, indicating the incorporation of Pt and the formation of a small portion of Ni3Pt alloy on the catalyst particle surface. In Ni3Ga... 0.8 Pt 0.2 / CC and Ni3Pt 0.2 The X-ray diffraction pattern of / CC shows diffraction peaks at 2θ = 42.2° and 49.2°, corresponding to the diffraction peaks of Ni3Pt (PDF#01-01-0091). This is consistent with... Figure 2 The results are consistent with those obtained from the transmission electron microscopy (TEM) images.

[0088] To further investigate the surface chemical composition, metallic composition, and electronic states of the catalyst, Ni3Ga... 0.8 Pt 0.2 / CC catalysts were further characterized by X-ray photoelectron spectroscopy (XPS) as follows: Figure 4 As shown, (a) Ni 2p, (b) Ga 2p, and (c) Pt 4f plots are presented. The study of the catalytic system involves complex and diverse interactions, among which the electronic interactions between the supported Ni, Ga, and Pt trimetallic elements are crucial. Adjusting the electronic structure of the elements can lower the binding energy of reaction intermediates, thereby improving the HER catalytic activity. According to... Figure 4 The results indicate that the interactions between the metals during the reduction process lead to electron transfer in Pt metal nanoparticles, particularly from Pt atoms to Ni metal particles. During the reduction reaction in the preparation process, Pt binds to a portion of Ni. This portion of Ni exhibits the ability to absorb electrons from Pt. After some electrons are absorbed by Ni atoms, Pt exhibits a lower reduced state, which can be observed by the position of the Pt 4f peak in XPS at 71.88 eV, corresponding to Ni atoms in a lower oxidation state. Simultaneously, during the reduction reaction, another portion of Ni binds to Ga. This portion of Ni exhibits the ability to transfer electrons from Ga. After some electrons are absorbed by Ga atoms, Ni exhibits a lower reduced state, which can be observed by the position of the Ga 2p peak in XPS at 1118.15 eV. The interaction between Ni and Ga gives Ni a relatively high valence state, which may reduce the hydrogen adsorption rate, promote a decrease in the binding energy of the reaction intermediate, and thus accelerate the HER process. In conclusion, intermetallic electron transfer plays a crucial role in the electronic structure and chemical properties of catalysts.

[0089] EXAFS was used to further verify the existence of electron transfer between metals. Figure 5 (a) EXAFS spectra and (b) Fourier transforms of the catalysts prepared in Example 1 and Comparative Examples 2, 3, and 5. Figure 5 As shown in (a), in the energy range of 11550 eV to 11600 eV, compared with the catalysts prepared in Comparative Examples 2, 3, and 5, the Ni3Ga catalyst prepared in Example 1... 0.8 Pt 0.2 The / CC catalyst exhibits a weaker absorption signal. This is due to the interaction between Pt and carbon cloth, as well as electron transfer with Ni. Figure 5 (b) is approximately on the horizontal axis At this point, both curves exhibit different peaks, indicating the presence of Pt-Pt bonds within this distance range. At approximately [location missing] on the horizontal axis... At this point, all four curves show different peaks, indicating that the peaks in this range represent Pt-Pt bonds, but we can see Ni3Ga 0.8 Pt 0.2 / CC and Ni3Pt 0.2The Pt-Pt peaks of the / CC catalysts shifted, indicating an interaction between Ni and Pt. Meanwhile, in The peak appearing at this location indicates that Ni3Ga 0.8 Pt 0.2 There is a strong interaction between Pt and C in / CC, which is due to Ni3Ga 0.8 Pt 0.2 Electron transfer occurs between Pt and carbon cloth at the interface of / CC during the hydrogen evolution reaction caused by the passage of current.

[0090] Figure 6 EXAFS wavelet transform analysis of the platinum foils (a) and (b) of the catalyst prepared in Example 1. Figure 6 In the EXAFS wavelet transform analysis shown, Pt-C bonds appear in Ni3Ga 0.8 Pt 0.2 The position of the / CC catalyst on the specific abscissa represents the interaction between Pt and C. Ni-Pt bonds are also visible, representing electron transfer between Pt and Ni. The interaction between Pt and Ni can be better determined by comparing the wavelet transform spectra of the platinum foil.

[0091] Ni3Ga was studied in a conventional three-electrode electrolytic cell at room temperature. 0.8 Pt 0.2 / CC catalyst and its series of electrochemical HER properties. Using a mercury oxide electrode (HgO) as the reference electrode, 1cm 2 The Pt sheet electrode is used as the counter electrode, with Ni3Ga 0.8 Pt 0.2 Using the / CC catalyst as the working electrode and 1M KOH as the electrolyte, the test was conducted using a CHI760e electrochemical workstation from Shanghai Chenhua.

[0092] Test parameters: For linear voltammetry (LSV), the scan rate is 5 mV / s, and the scan range is -2 to -0.6 V relative to the reversible hydrogen electrode (RHE). For cyclic voltammetry, the scan rate is 50 mV / s, and the scan range is 0 to -5 V (relative to RHE).

[0093] The obtained potential is converted into the potential of the reversible hydrogen electrode (RHE) by the formula: E(RHE)=E(Hg / HgO)+0.098+0.059pH.

[0094] Table 1 shows the Ni3Ga content in 1M KOH solution. 0.8 Pt 0.2 / CC catalyst and other comparative samples' performance in producing hydrogen through water electrolysis. Figure 7Linear voltammetry (LSV) curves of the catalysts prepared in Examples 1 and Comparative Examples 2-5 are shown. Figure 7 It can be seen that Ni3Ga 0.8 Pt 0.2 The / CC catalyst has the lowest overpotential of 26mV, which is superior to the 54mV of commercial Pt / C; Ni3Pt 0.2 The overpotential of the / CC catalyst is 51mV, which is close to the 54mV of commercial Pt / C, while Ga... 0.8 Pt 0.2 The / CC catalyst exhibits a high overpotential, likely due to Ni, as a transition metal, providing more empty orbitals, generating back-bonding, and promoting electron transfer, thereby enhancing the catalyst's electrocatalytic performance. The Tafel slopes calculated in Table 1 reveal that Ni3Ga... 0.8 Pt 0.2 The / CC curve is smoother and has the smallest slope of 20.78 mV·dec -1 Superior to 38.35 mV·dec for commercial Pt / C -1 .

[0095] Table 1. HER performance of the catalysts prepared in Example 1 and Comparative Examples 2-5 under 1M KOH environment.

[0096]

[0097] The corresponding overpotential refers to the current density at 10 mA / cm². 2 The overpotential at that time; mV / dec represents the change in potential when the current density changes by an order of magnitude, where dec is an abbreviation for decade.

[0098] Figure 8 Table 2 shows the Ni3Ga prepared in Example 1. 0.8 Pt 0.2 LSV comparison of / CC and Pt / C in Comparative Example 5 under alkaline simulated seawater (1M KOH + 0.1M NaCl). From Figure 8 It can be seen that Ni3Ga 0.8 Pt 0.2 / CC at 10mA cm -2 The overpotential at current density is 25 mV, which is better than the 38 mV of commercial Pt / C. Furthermore, based on the Tafel slope calculated in Table 2, Ni3Ga... 0.8 Pt 0.2 / CC exhibits a lower Tafel slope compared to commercial Pt / C, and from the above data, Ni3Ga... 0.8 Pt 0.2 The / CC electrocatalyst outperforms commercial Pt / C in the electrolysis of simulated seawater.

[0099] Table 2. HER performance of the catalysts prepared in Example 1 and Comparative Example 5 under alkaline simulated seawater conditions.

[0100]

[0101] a) The corresponding overpotential refers to the current density of the preceding current being 10 mA / cm². 2 The overpotential at that time; mV / dec represents the change in potential when the current density changes by an order of magnitude, where dec is an abbreviation for decade.

[0102] Figure 9 Table 3 shows a comparison of the LSV of the catalysts prepared in Example 1 and Comparative Examples 6 and 7 under 1M KOH conditions. In contrast, Ni3Ga... 0.8 Pt 0.2 / CC at 10mAcm -2 The overpotential at the lowest current density is significantly lower than that of Ni3Ga. 0.7 Pt 0.3 / CC and Ni3Ga 0.9 Pt 0.1 / CC, from which we can conclude that the optimal molar ratio of Ni:Ga:Pt is 3:0.8:0.2.

[0103] Table 3. HER performance of the catalysts prepared in Example 1 and Comparative Examples 6 and 7 under 1M KOH environment.

[0104]

[0105] a) The corresponding overpotential refers to the current density of the preceding current being 10 mA / cm². 2 The overpotential at that time.

[0106] Figure 10 Table 4 shows the LSV comparison of the catalysts prepared in Example 1 and Comparative Examples 8 and 9 in 1M KOH solution. With increasing tube furnace calcination temperature, the degree of metal reduction in a hydrogen-nitrogen mixed atmosphere affects the electrochemical activity of the catalysts. Specifically, Ni3Ga... 0.8 Pt 0.2 / CC exhibits optimal electrochemical activity and the lowest overpotential after calcination at 700℃. Based on the above data, Ni3Ga... 0.8 Pt 0.2 The optimal calcination temperature for the / CC electrocatalyst is 700℃.

[0107] Table 4. HER performance of the catalysts prepared in Example 1 and Comparative Examples 8 and 9 under 1M KOH environment.

[0108]

[0109] a) The corresponding overpotential refers to the current density of the preceding current being 10 mA / cm². 2 The overpotential at that time.

[0110] Figure 11 Table 5 shows the LSV comparison of the catalysts prepared in Example 1 and Comparative Example 10 in 1M KOH solution, Ni3Ga 0.8 Pt 0.2 / CC at 10mAcm -2 The overpotential at current density is 25mV, which is better than that of Ni3Ga. 0.8 Pt 0.2 / NF 76mV. During the hydrogen evolution reaction, current flows through Ni3Ga 0.8 Pt 0.2 Electron transfer induced between Pt and carbon cloth at the / CC interface leads to a strong interaction between the Pt sites and the carbon cloth. This allows Ni3Ga 0.8 Pt 0.2 / CC electrocatalyst has better electrochemical performance than Ni3Ga 0.8 Pt 0.2 / NF.

[0111] Table 5. HER performance of the catalysts prepared in Example 1 and Comparative Example 10 under 1M KOH environment.

[0112]

[0113] a) The corresponding overpotential refers to the current density of the preceding current being 10 mA / cm². 2 The overpotential at that time.

[0114] The above embodiments are only used to explain the technical solutions provided by the present invention and are not intended to limit the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the technical solutions of the present invention.

Claims

1. A Ni3Ga 0.8 Pt 0.2 / CC catalyst, characterized in that, Including carbon cloth and Ni3Ga supported on carbon cloth 0.8 Pt 0.2 catalyst; The Ni3Ga 0.8 Pt 0.2 The preparation method of / CC catalyst includes the following steps: (1) The carbon cloth, nickel source, gallium source and platinum source are mixed and then impregnated in water to obtain a mixture; (2) The mixture was dried and reduced to obtain Ni3Ga 0.8 Pt 0.2 / CC catalyst; In step (1), the molar ratio of Ni / Ga / Pt in the nickel source, gallium source and platinum source is 3.0:0.8:0.2; In step (2), the reduction temperature is 700℃, the time is 2h, and the atmosphere is a hydrogen-nitrogen mixture with a volume ratio of 10%.

2. The Ni3Ga according to claim 1 0.8 Pt 0.2 / CC catalyst, characterized in that, The Ni3Ga 0.8 Pt 0.2 / CC catalyst Ni3Ga 0.8 Pt 0.2 The catalyst loading was 55-60 wt%, with Ni, Ga, and Pt loadings of 30-40 wt%, 10-15 wt%, and 10-15 wt%, respectively. The Ni3Ga 0.8 Pt 0.2 The / CC catalyst has a particle size of 150-250 nm.

3. The Ni3Ga according to claim 2 0.8 Pt 0.2 / CC catalyst, characterized in that, The Ni3Ga 0.8 Pt 0.2 / CC catalyst Ni3Ga 0.8 Pt 0.2 The catalyst loading was 57 wt%, with Ni, Ga, and Pt loadings of 35 wt%, 12 wt%, and 10 wt%, respectively. The Ni3Ga 0.8 Pt 0.2 The / CC catalyst has a particle size of 200 nm.

4. A Ni3Ga according to any one of claims 1-3 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, Includes the following steps: (1) The carbon cloth, nickel source, gallium source and platinum source are mixed and then impregnated in water to obtain a mixture; (2) The mixture was dried and reduced to obtain Ni3Ga 0.8 Pt 0.2 / CC catalyst; In step (1), the molar ratio of Ni / Ga / Pt in the nickel source, gallium source and platinum source is 3.0:0.8:0.2; In step (2), the reduction temperature is 700℃, the time is 2h, and the atmosphere is a hydrogen-nitrogen mixture with a volume ratio of 10%.

5. The Ni3Ga according to claim 4 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (1), the impregnation is ultrasonic dispersion for 10-30 min and impregnation for 10-15 h.

6. The Ni3Ga according to claim 5 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (1), the impregnation is ultrasonic dispersion for 20 min and impregnation for 12 h.

7. The Ni3Ga according to claim 4 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (1), before mixing, the carbon cloth is pretreated. The pretreatment method is to soak the carbon cloth in a mixed solution of acetone and ethanol, vacuum dry it, then soak it in sulfuric acid solution, wash it with water until neutral, and finally vacuum dry it.

8. The Ni3Ga according to claim 7 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (1), the pretreatment method is as follows: the soaking temperature is 25-30℃, the volume ratio of acetone to ethanol is 1:(1-3), the vacuum drying temperature is 55-60℃, the vacuum drying time is 10-12h, and the sulfuric acid solution is a solution of sulfuric acid and water with a volume ratio of 1:(1-2).

9. The Ni3Ga according to claim 4 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (1), the nickel source is one or more of nickel nitrate, nickel chloride, and nickel sulfate; The gallium source is one or more of gallium nitrate, gallium chloride, and gallium sulfate; The platinum source is one or more of chloroplatinic acid, potassium chloroplatinate, and platinum acetylacetonate.

10. The Ni3Ga according to claim 4 0.8 Pt 0.2 The method for preparing / CC catalyst is characterized by, In step (2), the drying temperature is 80-120℃ and the time is 10-15h.

11. A Ni3Ga according to any one of claims 1-3 0.8 Pt 0.2 Application of / CC catalyst in hydrogen production by water electrolysis.

12. The application according to claim 11, characterized in that, The water in question is simulated seawater.

13. The application according to claim 12, characterized in that, The simulated seawater is water containing 1M KOH and 0.1M NaCl.

14. A method for producing hydrogen by electrolysis of water, characterized in that, The Ni3Ga according to any one of claims 1-3 0.8 Pt 0.2 / CC catalyst was used as a catalyst for hydrogen production by water electrolysis in a 1M KOH environment.

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