A triatomic catalyst integrated electrode, a preparation method and application thereof
By spraying pyrazole precursor and metal salt solution onto carbon cloth or carbon paper to generate an integrated electrode of three-atom catalyst, the problems of high cost of precious metal catalysts and complex process of multi-atom catalysts are solved, achieving efficient and stable electrocatalytic performance and a simplified preparation process.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WUHAN TEXTILE UNIV
- Filing Date
- 2026-02-10
- Publication Date
- 2026-05-29
AI Technical Summary
Existing noble metal catalysts for oxygen reduction reactions suffer from high cost, limited resources, and insufficient durability. Furthermore, existing polyatomic catalysts have complex preparation processes and difficult-to-control active site distribution, while electrocatalysts are unstable when bonded to conductive substrates.
A pyrazole precursor monomer and metal salt solution are uniformly sprayed onto carbon cloth or carbon paper using a spraying process, generating a three-atom catalyst at room temperature. This directly forms a firmly bonded integrated electrode of the three-atom catalyst on a conductive substrate, avoiding the need for high-temperature heat treatment and the use of binders.
It achieves stable bonding between the catalyst and the substrate, improves electron conduction rate and structural stability, simplifies the preparation process, is suitable for flexible and large-area electrodes, and exhibits excellent catalytic activity and electrochemical performance.
Smart Images
Figure CN122117930A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrode technology, and in particular to an integrated three-atom catalyst electrode, its preparation method, and its application. Background Technology
[0002] With the development of electrochemical energy conversion technologies such as fuel cells and metal-air batteries, efficient and stable electrocatalysts play a crucial role in the oxygen reduction reaction (ORR) and related electrochemical reactions. While existing noble metal catalysts exhibit high catalytic activity, their high cost, limited resources, and insufficient durability restrict their large-scale application. Therefore, the development of high-performance non-noble metal electrocatalysts has become a key research focus in this field.
[0003] In recent years, single-atom and multi-atom catalysts have attracted attention due to their high atom utilization and tunable active structures. Among them, multi-atom catalysts have shown promising application prospects in electrocatalytic reactions through the synergistic effect between metal atoms. However, the preparation of existing multi-atom catalysts usually relies on high-temperature heat treatment or multi-step synthesis processes, which have problems such as high energy consumption, complex processes, and difficulty in precisely controlling the structure and distribution of active sites.
[0004] Furthermore, existing electrocatalysts are mostly loaded onto the surface of conductive substrates via coating, which typically requires the introduction of binders. This can easily increase interfacial resistance and affect the structural stability and electron transport efficiency of the catalyst. Therefore, there is an urgent need for an integrated electrode fabrication method that is simple to prepare, has a controllable structure, and can achieve a stable bond between the catalyst and the conductive substrate. Summary of the Invention
[0005] The purpose of this invention is to address the aforementioned shortcomings of the prior art by proposing an integrated three-atom catalyst electrode, its preparation method, and its application.
[0006] The first objective of this invention is to provide a method for preparing an integrated three-atom catalyst electrode, wherein a pyrazole precursor monomer and a metal salt are dissolved in a solvent to obtain a pyrazole precursor solution and a metal precursor solution, respectively; then the two solutions are sequentially and uniformly sprayed onto carbon cloth or carbon paper, and allowed to stand and solidify at room temperature to obtain the integrated three-atom catalyst electrode. The pyrazole precursor monomer is 2,4,6-tris(4-(1H-pyrazole-4-yl)phenyl)-1,3,5-triazine and / or 1,3,5-tris(1H-pyrazole-4-yl)phenyl; The metal is one or more of Co, Fe, Mn, and Ni.
[0007] Furthermore, the molar ratio of the pyrazole precursor monomer and the metal salt sprayed onto the carbon cloth or carbon paper is 3:1.
[0008] Furthermore, the concentration of the pyrazole precursor solution was 0.00375~0.00480 mol / L.
[0009] Furthermore, the concentration of the metal precursor solution is 0.00125~0.00160 mol / L.
[0010] Furthermore, the metal salt is an acetate.
[0011] Furthermore, the solvent is one or a mixture of two of DMF, methanol, DCM, and ethanol.
[0012] Furthermore, the combined mass of the pyrazole precursor monomer and the metal salt is sprayed onto carbon cloth or carbon paper at a rate of 2-4 mg / cm³. 2 .
[0013] A second objective of this invention is to provide an integrated electrode for a three-atom catalyst prepared using the above-described preparation method.
[0014] A third object of the present invention is to provide an application of the three-atom catalyst integrated electrode as described above, characterized in that it is used as the negative electrode of a zinc-air battery.
[0015] This invention employs a spraying process to achieve uniform loading, enabling uniform dispersion and synchronous reaction of the catalyst precursor and metal source on the substrate surface, avoiding agglomeration and improving the uniformity of catalytic site distribution. Utilizing the high reactivity of pyrazole monomers, a triatomic catalyst is directly generated at room temperature under the traction of metal ions. This room-temperature in-situ synthesis eliminates the need for high-temperature heat treatment, saving energy and preventing structural collapse.
[0016] This invention features an integrated electrode structure where the catalyst is directly grown on the surface of a conductive substrate, forming a strong chemical / physical bond. This avoids the use of binders and improves electron conduction rate and structural stability.
[0017] The present invention has strong structural tunability: the electronic structure and conjugation degree of the catalyst can be adjusted by changing the substituents of the pyrazole monomer; the catalytic performance can be directionally regulated by changing the metal type, adapting to different catalytic reactions (such as OER, HER, ORR, CO2 reduction, etc.).
[0018] The preparation method of the present invention is applicable to flexible and large-area electrodes: the spraying method is simple, easy to scale up, and can be prepared on flexible carbon cloth or rigid carbon paper, making it suitable for the mass production of flexible devices and large-area electrodes.
[0019] The three-atom catalyst integrated electrode prepared by this invention has excellent catalytic activity. When assembled into a zinc-air battery, the battery exhibits excellent electrochemical performance. Attached Figure Description
[0020] Figure 1 This is a schematic diagram of the preparation method of the present invention; Figure 2 This is a schematic diagram of the synthesis of the three-atom catalyst prepared in Example 1; Figure 3 This is a schematic diagram of the structure of the three-atom catalyst prepared in Example 1; Figure 4 This is a schematic diagram of the synthesis of the three-atom catalyst prepared in Example 2; Figure 5 This is a schematic diagram of the structure of the three-atom catalyst prepared in Example 2; Figure 6 LSV curves of different metal element catalysts prepared in Example 1; Figure 7 LSV curves of two different metal element catalysts prepared in Example 1; Figure 8 LSV curves of different metal element catalysts prepared in Example 2; Figure 9 Open-circuit voltage of zinc-air battery fabricated using Co3@KB integrated electrode; Figure 10 A comparison of the power densities of zinc-air batteries prepared with Co3@KB integrated electrode and Pt / C; Figure 11 Comparison of rate performance of zinc-air batteries prepared with Co3@KB integrated electrode and Pt / C. Detailed Implementation
[0021] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings. However, the present invention is not limited to these embodiments.
[0022] Example 1 Preparation of integrated electrode for triatomic catalyst: First, metal acetate M (cobalt acetate, ferrous acetate, manganese acetate, nickel acetate) was dissolved in DMF to form a metal precursor solution (concentration: 0.00156 mol / L). Separately, pyrazole monomer 2,4,6-tris(4-(1H-pyrazole-4-yl)phenyl)-1,3,5-triazine was dissolved in DMF to form a pyrazole precursor solution (concentration: 0.00469 mol / L). Then, the two solutions were separately loaded into two reservoirs of a spray gun and simultaneously sprayed onto the surface of a conductive substrate (such as carbon cloth or carbon paper) at room temperature.
[0023] During the spraying process, the two precursors come into contact on the substrate and react rapidly, generating a three-atom catalyst with a [M3N6] planar structure in situ through metal ion-induced coordination (as shown in the schematic diagram of its synthesis). Figure 2 As shown, the synthesized structural formula is as follows: Figure 3 As shown in the figure, it is firmly attached to the substrate to form an integrated electrode. After the coating is completed, the electrode is left to cure at room temperature without subsequent heat treatment or washing steps, thus obtaining a ready-to-use integrated electrode for the three-atom catalyst.
[0024] M is selected from one of Co, Fe, Mn, and Ni, or a combination of CoNi (molar ratio 2:1), CoCu (molar ratio 2:1), CoFe (molar ratio 2:1), CoMn (molar ratio 2:1), and MnNi (molar ratio 2:1). The resulting triatomic catalyst integrated electrode is denoted as Tz-Co3@KB, Tz-Fe3@KB, Tz-Mn3@KB, Tz-Ni3@KB, Tz-CoNi@KB, Tz-CoFe @KB, Tz-CoMn @KB, and Tz-MnNi@KB.
[0025] Example 2 The monomer in Example 1 was replaced with 1,3,5-tris(1H-pyrazol-4-yl)phenyl, and M was selected from Co, Fe, Mn, and Ni, respectively. All other parameters remained the same as in Example 1. A three-atom catalyst with a [M3N6] planar structure was generated in situ (its synthesis schematic is shown in Figure 1). Figure 4 As shown, the synthesized structural formula is as follows: Figure 5 As shown), the resulting integrated three-atom catalyst electrodes are denoted as TP-Co3@KB, TP-Fe3@KB, TP-Mn3@KB, TP-Ni3@KB, TP-CoNi@KB, TP-CoFe@KB, TP-CoMn@KB, and TP-MnNi@KB.
[0026] Experimental testing process: The obtained triatomic catalysts were ground into a mortar until they formed a uniform and fine powder. 3 mg of the catalyst powder was weighed and placed in a 3 mL sample vial. 475 μL of anhydrous ethanol and 25 μL of Nafion were added to form a slurry. The slurry was then sonicated for 30 min to ensure uniform dispersion of the catalyst in the solvent. 10 μL of the slurry was pipetted onto the electrode, allowed to stand, and then air-dried. The slurry was then heated at 0.1 mol·L⁻¹. -1 The test was conducted in NaOH electrolyte. The reaction conditions were: 0.1 mol·L⁻¹ -1 NaOH electrolyte was saturated with O2, and linear sweep voltammetry curves were obtained at room temperature by scanning at 400 / 625 / 900 / 1225 / 1600 rpm and 10 mV / s.
[0027] Weigh 3 mg of Pt / C catalyst powder into a 3 mL sample vial, add 475 μL of anhydrous ethanol and 25 μL of Nafion to prepare a slurry, and sonicate in an ultrasonicator for 30 min to ensure uniform dispersion of the catalyst in the solvent. Use a pipette to drop 167 μL of the slurry onto carbon cloth / paper, allow it to stand, and air dry to serve as the cathode. [The last sentence appears to be incomplete and requires further context.] -1 The test was conducted in NaOH electrolyte. The reaction conditions were: 0.1 mol·L⁻¹ -1 NaOH electrolyte was saturated with O2, and linear sweep voltammetry curves were obtained at room temperature by scanning at 400 / 625 / 900 / 1225 / 1600 rpm and 10 mV / s.
[0028] Figure 6 The LSV curve of the integrated electrode of the triatomic catalyst of a single metal element prepared in Example 1.
[0029] from Figure 6 It can be seen that, except for the poor performance of the copper catalyst (indicating that copper is not suitable for the ORR process), the half-wave potentials of the other metal catalysts are all in the range of 0.90-0.93 V, which is significantly higher than that of commercial platinum-carbon catalysts.
[0030] Figure 7 The LSV curves are for the integrated electrodes of two different metal elements with three-atom catalysts prepared in Example 1.
[0031] from Figure 7 It can be seen that, except for the integrated electrode prepared with copper catalyst, which has poor performance (indicating that copper is not suitable for the ORR process), the half-wave potential of the integrated electrodes of the other triatomic catalysts is 0.90-0.95 V, which is significantly higher than that of commercial platinum-carbon catalysts and slightly higher than that of homonuclear triatomic catalysts.
[0032] Figure 8 The LSV curves of the integrated electrode of three-atom catalysts with different metal elements prepared in Example 2.
[0033] from Figure 8 It can be seen that, except for the integrated electrode prepared with copper catalyst, which has poor performance (indicating that copper is not suitable for the ORR process), the half-wave potential of the integrated electrodes of the other three-atom catalysts is between 0.89 and 0.92 V, which is significantly higher than that of commercial platinum-carbon catalysts.
[0034] Experimental testing process: The triatomic catalyst integrated electrode Tz-Co3@KB prepared in Example 1 was used as the cathode to assemble a zinc-air battery for testing. The electrolyte was a mixture of 6.0 M KOH and 0.2 M Zn(OAc)2. All measurements were performed at room temperature on a CHI760E electrochemical workstation.
[0035] Test results are as follows Figure 9-11 As shown in the figure, the measured open-circuit voltage of the battery can reach 1.56 V; the power density can reach 130.7 mW / cm². -2 The performance is far superior to that of Pt / C-zinc-air batteries prepared by traditional methods; the rate performance test results are still better than those of Pt / C-zinc-air batteries.
[0036] For any points not covered above, existing technologies shall apply.
[0037] Although specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, without departing from the direction of the invention or exceeding the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc., made to the above embodiments based on the technical essence of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing an integrated electrode with a three-atom catalyst, characterized in that, The pyrazole precursor monomer and the metal salt are dissolved in a solvent to obtain a pyrazole precursor solution and a metal precursor solution, respectively; then the two solutions are uniformly sprayed onto carbon cloth or carbon paper in sequence and allowed to stand and solidify at room temperature to obtain the integrated electrode of the three-atom catalyst. The pyrazole precursor monomer is 2,4,6-tris(4-(1H-pyrazole-4-yl)phenyl)-1,3,5-triazine and / or 1,3,5-tris(1H-pyrazole-4-yl)phenyl; The metal is one or more of Co, Fe, Mn, and Ni.
2. The preparation method according to claim 1, characterized in that, The molar ratio of pyrazole precursor monomer and metal salt sprayed onto the carbon cloth or carbon paper is 3:
1.
3. The preparation method according to claim 1, characterized in that, The concentration of the pyrazole precursor solution was 0.00375~0.00480 mol / L.
4. The preparation method according to claim 1, characterized in that, The concentration of the metal precursor solution was 0.00125~0.00160 mol / L.
5. The preparation method according to claim 1, characterized in that, The metal salt is an acetate.
6. The preparation method according to claim 1, characterized in that, The solvent is one or a mixture of two of DMF, methanol, DCM, and ethanol.
7. The preparation method according to claim 1, characterized in that, The combined mass of the pyrazole precursor monomer and the metal salt, when sprayed onto carbon cloth or carbon paper, is 2-4 mg / cm³. 2 .
8. A three-atom catalyst integrated electrode prepared by the preparation method according to any one of claims 1-7.
9. An application of the integrated three-atom catalyst electrode as described in claim 8, characterized in that, Used as the negative electrode in zinc-air batteries.