A method based on SO4 2- Catalysts for Modified Nanoalloys Composite with Nitrogen and Sulfur Co-doped One-Dimensional Carbon and Their Preparation Methods

Abstract

The application discloses a kind of based on SO4 2‑ The application discloses a catalyst of modified nano-alloy and nitrogen and sulfur co-doped one-dimensional carbon composite and a preparation method thereof, and belongs to the field of new energy battery materials.In the catalyst of the application, SO4 2‑ The modified non-noble metal nano-alloy is in-situ grown as a new type of high-activity center on the nitrogen and sulfur co-doped one-dimensional carbon nanomaterial.SO4 2‑ The alloy in the modified nano-alloy is a binary or multi-alloy formed by two or more than three of non-noble metals Co, Fe, Ni, Cu and Mn (including but not limited to), and the alloy has a spherical shape with a diameter of 5-300 nanometers.The nitrogen and sulfur co-doped carbon nanomaterial has a one-dimensional shape with a wrinkled surface, and the one-dimensional material has a diameter of 50-500 nanometers.The synergistic effect of the composite catalyst greatly improves the activity and stability of electrocatalytic reactions such as oxygen reduction reaction, oxygen evolution reaction and carbon dioxide reduction.

Description

Technical Field

[0001] This invention relates to the field of new energy battery materials, specifically to a method based on SO4. 2- Catalysts for modifying nanoalloys with nitrogen and sulfur co-doped one-dimensional carbon composites and their preparation methods. Background Technology

[0002] Environmental pollution and energy shortages have become two major problems that cannot be ignored by human society. Fuel cells and zinc-air batteries, as clean and efficient new energy technologies, have attracted much attention. However, the relatively sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode in fuel cells and zinc-air batteries pose a significant challenge to their commercialization, making them a major obstacle to their development. Therefore, developing ORR and OER catalysts with high catalytic performance, good stability, and low cost is currently a research hotspot in the field of fuel cells and zinc-air batteries.

[0003] Currently, commercially available ORR and OER catalysts are mainly noble metals such as Pt and RuO2, exhibiting high electrocatalytic activity. However, they also suffer from drawbacks such as raw material scarcity, high cost, and poor long-cycle stability. In recent years, non-noble metals and their nanoalloys have attracted considerable attention from researchers as highly efficient ORR and OER catalysts. These catalysts based on non-noble metal active centers have advantages such as low cost, low overpotential, and high stability, making them the best choice to completely replace noble metals Pt and RuO2. Generally, the main methods to improve the catalytic performance of non-noble metal-based nanomaterials are alloying, morphology modification, and composite support modification. That is, by combining different types of non-noble metals, such as Ni, Fe, and Co, to form binary or multi-component nanoalloys, and then combining these nanoalloys with different supports, such as carbon materials and TiO2, their catalytic activity and stability can be further enhanced.

[0004] Chinese invention patent CN202011455086 discloses a method for preparing NiFe LDH@Super-P composite electrocatalytic materials. This invention enables NiFe LDH to expose more active sites and utilizes the high conductivity of Super-P to improve electron migration rate, effectively overcoming the problem of poor conductivity of NiFe LDH and enhancing the catalytic activity and stability of the composite electrocatalytic material.

[0005] Chinese invention patent CN202110454977 discloses a C3N4-coated carbon nanotube-supported NiFe bifunctional oxygen electrocatalyst and its preparation method. This invention uses carbon nanotubes as the carbon framework, with NiFe embedded within the carbon framework in the form of nano-metal particles. Simultaneously, the carbon nanotubes are coated with C3N4. It exhibits excellent dual electrocatalytic activity for both oxygen efflux (OER) and oxygen efflux (ORR) in alkaline media. The preparation method is simple and has good application potential in practical energy conversion devices.

[0006] Chinese invention patent CN202010333222 discloses a core-shell structured carbon-coated nano-CoFe alloy oxygen evolution catalyst. The CoFe alloy is uniformly dispersed in a graphitized porous carbon matrix, avoiding the agglomeration of the nano-CoFe alloy and facilitating the full exposure of electrochemical active sites. The core-shell structure and numerous pores facilitate sufficient wetting of the electrolyte and full contact with the electrochemical active sites.

[0007] Chinese invention patent CN202210532317 discloses a CoNi alloy MOF porous material. This invention can obtain product particles with good dispersibility and uniform morphology and particle size. After high-temperature reduction under a nitrogen atmosphere, the particles can still maintain their original morphology relatively intact, without obvious agglomeration. Furthermore, this CoNi alloy MOF porous material exhibits excellent performance in microwave absorption, catalysis, and sensors.

[0008] In summary, despite extensive research on carbon-supported non-precious metal nanoalloy catalysts, there is still significant room for improvement in their catalytic activity and stability. The microstructure and morphology of non-precious metal nanoalloys and carbon nanomaterials require precise control to obtain catalysts with superior performance. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention proposes a method based on SO4. 2- Catalysts for modifying nanoalloys with nitrogen and sulfur co-doped one-dimensional carbon composites and their preparation methods.

[0010] The objective of this invention can be achieved through the following technical solutions:

[0011] A first aspect of the present invention relates to a catalyst comprising:

[0012] Nitrogen and sulfur co-doped one-dimensional carbon nanomaterials; and

[0013] SO4 grown in situ on the one-dimensional carbon nanomaterial 2- Modified nano-alloys, SO4 2- Molecular groups are bonded to nanoalloys via chemical or physical bonds.

[0014] Optionally, the one-dimensional carbon nanomaterial has surface wrinkles.

[0015] Optionally, the diameter of the one-dimensional carbon nanomaterial is 50-500 nanometers.

[0016] Optionally, the nanoalloy is an alloy formed from any combination of Co, Fe, Ni, Cu, and Mn.

[0017] Optionally, the nanoalloy has a spherical morphology with a diameter of 5-300 nanometers.

[0018] A second aspect of the present invention relates to a method for preparing a catalyst, comprising the following steps:

[0019] Melamine and two or more non-precious metal sulfates are added to deionized water, ultrasonicated to form a homogeneous emulsion, and stirred to obtain a mixture of melamine and non-precious metal sulfates.

[0020] The mixture was dried by freeze-drying.

[0021] The dried sample was calcined under gas protection, and after calcination, the sample was cooled to room temperature to obtain the catalyst.

[0022] Optionally, the non-precious metal sulfate is a mixture of various sulfates of Co, Fe, Ni, Cu, and Mn.

[0023] Optionally, the calcination step specifically involves calcining at 700°C and 800°C successively.

[0024] Optionally, the heating rate during the calcination process is 6°C·min. -1 .

[0025] A third aspect of the present invention relates to the use of the above-described catalyst in the preparation of fuel cells or metal-air batteries.

[0026] The beneficial effects of this invention are:

[0027] Compared with existing commercial catalysts, the catalyst prepared by this invention has a synergistic effect that significantly improves the activity and stability of electrocatalytic reactions such as oxygen reduction reaction, oxygen evolution reaction, and carbon dioxide reduction. Attached Figure Description

[0028] The invention will now be further described with reference to the accompanying drawings.

[0029] Figure 1 SO4 in Embodiment 1 of this application 2- - S 2p XPS high-resolution spectrum of NiFe / NSCT composite catalyst.

[0030] Figure 2 SO4 in Embodiment 1 of this application 2- Scanning electron microscope image of the NiFe / NSCT composite catalyst.

[0031] Figure 3 SO4 in Embodiment 1 of this application 2- XRD pattern of the NiFe / NSCT composite catalyst.

[0032] Figure 4 SO4 in Embodiment 1 of this application 2- - Oxygen reduction reaction activity of NiFe / NSCT composite catalyst and commercial Pt / C catalyst.

[0033] Figure 5 SO4 in Embodiment 1 of this application 2- - Oxygen evolution reaction activity of NiFe / NSCT composite catalyst and commercial RuO2 catalyst.

[0034] Figure 6 SO4 in Embodiment 4 of this application 2- Scanning electron microscope image of the -CoFe / NSCT composite catalyst.

[0035] Figure 7 SO4 in Embodiment 4 of this application 2- XRD pattern of the CoFe / NSCT composite catalyst.

[0036] Figure 8 SO4 in Embodiment 4 of this application 2- -Oxygen reduction reaction activity of CoFe / NSCT composite catalyst and commercial Pt / C catalyst.

[0037] Figure 9 SO4 in Embodiment 4 of this application 2- -Oxygen evolution reaction activity of CoFe / NSCT composite catalyst and commercial RuO2 catalyst. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] 20 g of melamine, 1.5 g of nickel sulfate, and 1.5 g of ferrous sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 hours to obtain a melamine-nickel sulfate-ferrous sulfate mixture. The mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 hours, followed by a second calcination at 800 °C for 2 hours. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -NiFe / NSCT composite catalyst. SO4 2- The S 2p XPS high-resolution spectrum of the NiFe / NSCT composite catalyst is as follows: Figure 1 As shown, this indicates the formation of SO4. 2- Modified NiFe alloys and nitrogen-sulfur co-doped carbon nanomaterials. SO4 2- The morphology of the NiFe / NSCT composite catalyst is as follows: Figure 2 As shown. SO4 2- The crystal structure of the NiFe / NSCT composite catalyst is as follows: Figure 3 As shown. Figure 4 The image shows SO4. 2- The oxygen reduction reaction activity of the NiFe / NSCT composite catalyst and the commercial Pt / C catalyst indicates that SO42- 2- The NiFe / NSCT composite catalyst exhibits higher oxygen reduction reaction activity than commercial Pt / C catalysts. Figure 5 The image shows SO4. 2- The oxygen evolution reaction activity of the NiFe / NSCT composite catalyst and the commercial RuO2 catalyst indicates that SO42- 2- The NiFe / NSCT composite catalyst exhibits higher oxygen evolution reaction activity than the commercial RuO2 catalyst.

[0041] Example 2

[0042] 20 g of melamine, 1.0 g of nickel sulfate, and 1.0 g of ferrous sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 h to obtain a melamine-nickel sulfate-ferrous sulfate mixture. The mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 h, followed by a second calcination at 800 °C for 2 h. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -NiFe / NSCT-2 composite catalyst. Tests show that SO4... 2-The NiFe / NSCT-2 composite catalyst exhibits superior activity in both oxygen reduction and oxygen evolution reactions compared to commercial Pt / C and RuO2.

[0043] Example 3

[0044] 20 g of melamine, 2.0 g of nickel sulfate, and 2.0 g of ferrous sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 hours to obtain a melamine-nickel sulfate-ferrous sulfate mixture. The mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 hours, followed by a second calcination at 800 °C for 2 hours. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -NiFe / NSCT-3 composite catalyst. Tests show that SO4... 2- The NiFe / NSCT-3 composite catalyst exhibits superior activity in both oxygen reduction and oxygen evolution reactions compared to commercial Pt / C and RuO2.

[0045] Example 4

[0046] 20 g of melamine, 1.5 g of ferrous sulfate, and 1.5 g of cobalt sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 hours to obtain a melamine-ferrous sulfate-cobalt sulfate mixture. The mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 hours, followed by a second calcination at 800 °C for 2 hours. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -CoFe / NSCT composite catalyst. SO4 2- The morphology of the -CoFe / NSCT composite catalyst is as follows: Figure 6 As shown. SO4 2- The crystal structure of the -CoFe / NSCT composite catalyst is as follows: Figure 7 As shown. Figure 8 The image shows SO4. 2- The oxygen reduction reaction activity of the -CoFe / NSCT composite catalyst and the commercial Pt / C catalyst indicates that SO42- 2- The oxygen reduction reaction activity of the -CoFe / NSCT composite catalyst is higher than that of commercial Pt / C catalyst. Figure 9 The image shows SO4. 2- The oxygen evolution reaction activity of the -CoFe / NSCT composite catalyst and the commercial RuO2 catalyst indicates that SO4 2-The -CoFe / NSCT composite catalyst exhibits higher oxygen evolution reaction activity than commercial RuO2 catalysts.

[0047] Example 5

[0048] 20 g of melamine, 1.5 g of nickel sulfate, and 1.5 g of cobalt sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 hours to obtain a melamine-nickel sulfate-cobalt sulfate mixture. The mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 hours, followed by a second calcination at 800 °C for 2 hours. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -NiCo / NSCT composite catalyst. Tests show that SO4... 2- The NiCo / NSCT composite catalyst exhibits superior activity in both oxygen reduction and oxygen evolution reactions compared to commercial Pt / C and RuO2.

[0049] Example 6

[0050] 20 g of melamine, 1.0 g of nickel sulfate, 1.0 g of ferrous sulfate, and 1.0 g of cobalt sulfate were added to 20 mL of deionized water and sonicated to form a homogeneous emulsion. The emulsion was then vigorously stirred at room temperature for 3 hours to obtain a mixture of melamine-nickel sulfate-ferrous sulfate-cobalt sulfate. The resulting mixture was then lyophilized. Under argon protection, the dried sample was calcined at 700 °C for 2 hours, followed by a second calcination at 800 °C for 2 hours. The heating rate throughout the calcination process was 6 °C / min. -1 After calcination, the sample is cooled to room temperature to obtain SO4. 2- -NiFeCo / NSCT composite catalyst. Tests show that SO4... 2- The NiFeCo / NSCT composite catalyst exhibits superior activity in both oxygen reduction and oxygen evolution reactions compared to commercial Pt / C and RuO2.

[0051] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0052] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A catalyst, characterized in that, include: Nitrogen- and sulfur-doped one-dimensional carbon nanomaterials; as well as SO4 grown in situ on the one-dimensional carbon nanomaterial 2- Modified nano-alloys, SO4 2- Molecular groups are bonded to nanoalloys via chemical or physical bonds. The method for preparing the catalyst includes the following steps: Melamine and two or more non-precious metal sulfates are added to deionized water, ultrasonicated to form a homogeneous emulsion, and stirred to obtain a mixture of melamine and non-precious metal sulfates. The mixture is dried by freeze-drying. The dried sample was calcined under a protective gas atmosphere, and after calcination, the sample was cooled to room temperature to obtain the catalyst.

2. The catalyst according to claim 1, characterized in that, The one-dimensional carbon nanomaterial has surface wrinkles.

3. The catalyst according to claim 1, characterized in that, One-dimensional carbon nanomaterials have a diameter of 50-500 nanometers.

4. The catalyst according to claim 1, characterized in that, The nano-alloy is an alloy formed from any combination of Co, Fe, Ni, Cu, and Mn.

5. The catalyst according to claim 1, characterized in that, The nanoalloy has a spherical shape with a diameter of 5-300 nanometers.

6. A method for preparing the catalyst according to claim 1, comprising the following steps: Melamine and two or more non-precious metal sulfates are added to deionized water, ultrasonicated to form a homogeneous emulsion, and stirred to obtain a mixture of melamine and non-precious metal sulfates. The mixture is dried by freeze-drying. The dried sample was calcined under a protective gas atmosphere, and after calcination, the sample was cooled to room temperature to obtain the catalyst.

7. The catalyst preparation method according to claim 6, characterized in that, Non-precious metal sulfates are mixtures of various sulfates of Co, Fe, Ni, Cu, and Mn.

8. The catalyst preparation method according to claim 6, characterized in that, The calcination step specifically involves calcining at 700 ℃ and 800 ℃ successively.

9. The catalyst preparation method according to claim 6, characterized in that, The heating rate during the calcination process is 6 °C·min. -1 .

10. The use of the catalyst according to any one of claims 1 to 5 in the preparation of fuel cells or metal-air batteries.

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