Polymer-based four-atom-cluster electrocatalyst material as well as preparation method and application thereof
By preparing polymer-based tetra-cluster electrocatalyst materials, the limitations of single-atom catalysts in terms of structural design and performance regulation have been overcome, achieving clear and controllable catalytic active sites and improving catalytic efficiency and adaptability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WUHAN TEXTILE UNIV
- Filing Date
- 2025-12-29
- Publication Date
- 2026-04-10
AI Technical Summary
Existing single-atom catalysts have limitations in structural design and performance regulation, making it difficult to simultaneously adapt to the adsorption requirements of different intermediates in multi-step reactions. Furthermore, the high-temperature pyrolysis process leads to metal agglomeration and structural disorder, which limits catalytic efficiency and reproducibility.
A polymer-based tetra-cluster electrocatalyst material preparation method was adopted, in which tetra-clusters were constructed on a carbon substrate through Schiff base reaction. The amino and aldehyde small molecule monomers were used to complex metal ions, avoiding high-temperature pyrolysis, forming a catalyst with a well-defined structure, enhancing the synergistic effect between metals, and regulating the adsorption/desorption behavior of reaction intermediates.
This approach achieves clarity and tunability of catalytic active sites, significantly improves the catalytic activity and adaptability of the catalyst, and optimizes mass transfer and activation performance under different reaction environments.
Smart Images
Figure CN121824873A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalyst technology, and in particular to a polymer-based four-atom cluster electrocatalyst material, its preparation method, and its application. Background Technology
[0002] In recent years, single-atom catalysts have shown great potential in clean energy conversion and other fields due to their unique atomically dispersed structure and near 100% atom utilization. For example, in the oxygen reduction reaction (ORR), single-atom catalysts, with their well-defined and highly uniform active sites, can precisely control the adsorption behavior of reaction intermediates, providing an ideal model system for deeply elucidating the adsorption mechanism and the structure-activity relationship of catalysis. However, single-atom catalysts still have inherent limitations in terms of structural design and performance regulation: a single active site cannot simultaneously adapt to the adsorption requirements of different intermediates in multi-step reactions, resulting in limited catalytic efficiency; in addition, the lack of effective electronic and spatial synergy between single-atom sites makes it impossible to further regulate the reaction pathway through intermetallic interactions.
[0003] Furthermore, existing preparation methods mostly rely on high-temperature pyrolysis. Although some strategies can anchor certain metal atoms during pyrolysis, metal agglomeration or structural disorder is still inevitable, leading to unclear active site structures, poor reproducibility, and difficulty in achieving accurate structure-activity relationship analysis and rational design. While the electronic structure of single-atom centers can be adjusted to some extent by controlling support defects and heteroatom doping, the control is limited, and it is impossible to systematically introduce multi-metal synergistic mechanisms, thus restricting further improvement of catalyst performance and application expansion.
[0004] Therefore, developing a novel catalyst system with a well-defined structure, tunable active sites, and the ability to utilize the synergistic effect of multiple metals has become a key direction for overcoming the performance bottleneck of single-atom catalysts. Summary of the Invention
[0005] The purpose of this invention is to address the aforementioned shortcomings of the prior art by proposing a polymer-based tetra-cluster electrocatalyst material, its preparation method, and its application.
[0006] The first objective of this invention is to provide a method for preparing a polymer-based four-atom cluster electrocatalyst material, wherein an amino small molecule monomer is added to a DMF solution of metal M1 to form an amino precursor mixture, and an aldehyde small molecule monomer is added to a DMF solution of metal M2 to form an aldehyde precursor mixture; the amino precursor mixture and the aldehyde precursor mixture are added to a DMF solution of a pre-uniformly dispersed carbon substrate, and a polymer-based four-atom cluster electrocatalyst material is formed by a Schiff base reaction; The amino small molecule monomer is one of 1,2,4,5-phenyltetramine (BTTA), 2,3,6,7-tetraaminonaphthalene (NTTA), anthracene-2,3,6,7-tetramine (ATTA), 4,5,9,10-tetraaminopyrene (PTTA), and 2,3,6,7,10,11-hexaaminotriphenyl (HATP); The aldehyde-based small molecule monomer is 1,10-phenanthroline-2,9-dicarboxaldehyde (PDA). M1 and M2 are one or more of Fe, Co, Ni, Cu, and Mn.
[0007] Furthermore, M1 and M2 are made of the same metal.
[0008] Furthermore, M1 and M2 are Fe or Co.
[0009] Furthermore, M1 and M2 are not the same.
[0010] Furthermore, M1 or M2 is Fe, and M2 or M1 is Co or Ni.
[0011] Furthermore, the carbon substrate includes one or more of the following: Ketjen black (KB), conductive carbon black, carbon nanotubes, activated carbon, graphene, carbon cloth, carbon fiber, cotton fabric, polyester, nylon, wool, silk, glass fiber cloth, aramid fiber cloth, and polypropylene.
[0012] Furthermore, the reaction temperature is 100-120 ℃, and the time is 1-5 days.
[0013] A second objective of this invention is to provide a polymer-based tetra-cluster electrocatalyst material prepared by the method described above.
[0014] A third objective of this invention is to provide an application of the polymer-based tetra-cluster electrocatalyst material as described above in oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), or carbon dioxide reduction reaction (CO2RR).
[0015] The present invention employs a simple "complexation-condensation" strategy: firstly, small monomers containing dinitrogen-coordinated amino or aldehyde groups are used to complex metal ions, and then the two monomers are condensed through a Schiff base reaction to construct a catalyst material with well-defined structural characteristics. This method eliminates the need for high-temperature pyrolysis, avoiding metal atom aggregation or structural uncertainty that may result from high temperatures, while also ensuring the clarity and tunability of the active site structure. Benefiting from the enhanced intermetallic synergistic effect within the four-atom clusters, this catalyst can precisely optimize the adsorption energy for different key reaction intermediates and synergistically regulate the adsorption / desorption behavior of these intermediates, thereby achieving significantly enhanced catalytic activity. Furthermore, by adjusting the amino monomers, the spacing between the four-atom clusters can be flexibly controlled, allowing it to better adapt to the mass transfer and activation requirements under different reaction environments. Attached Figure Description
[0016] Figure 1 Transmission electron microscopy image of Fe4-BTA@KB; Figure 2 Aberration-corrected transmission electron microscopy image of Fe4-BTA@KB catalyst; Figure 3 Linear sweep voltammetric curves of polymer-based homogeneous four-atom cluster catalysts (Fe4-BTA@KB, Co4-BTA@KB, Ni4-BTA@KB, Cu4-BTA@KB, Mn4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte.
[0017] Figure 4 Linear sweep voltammetric curves of polymer-based homo / heterogeneous tetra-cluster catalysts (Fe2Co2-B / PDA@KB, Fe4-BTA@KB, Co4-BTA@KB, Fe2Ni2-B / PDA@KB, Co2Ni2-B / PDA@KB, Ni4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte.
[0018] Figure 5 Linear sweep voltammetric curves of polymer-based heterogeneous four-atom cluster catalysts (Fe2Co2-B / PDA@KB, Co2Fe2-B / PDA@KB, Pt / C) in 0.1 M KOH electrolyte (different positions of the metals).
[0019] Figure 6 Linear sweep voltammetry curves of polymer-based homo / heterogeneous tetra-cluster catalysts (Fe2Co2-H / PDA@KB, Fe2Co2-B / PDA@KB, Fe4-HATP@KB, Fe4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte. Detailed Implementation
[0020] 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.
[0021] Example 1 Synthesis of Polymer-Based Homogeneous Tetra-Atom Cluster Electrocatalytic Materials First, FeCl2 was dispersed in two separate DMF solutions to form two FeCl2 DMF solutions. Then, 1,2,4,5-phenyltetramine monomer (BTTA) and 1,10-phenanthroline-2,9-dicarboxaldehyde monomer (PDA) were added to the two metal DMF solutions respectively to form a precursor mixture of amino and aldehyde groups for later use. Ketjen black was uniformly dispersed in DMF. After uniform dispersion, the precursor mixture of the two monomers was added to the DMF solution, and the reaction was carried out at 120 °C for 3 days using a solvothermal method. After the reaction was completed, filtration and washing were performed to obtain the polymer-based homogeneous tetra-atom cluster catalyst material Fe4-BTA@KB.
[0022] The remaining polymer-based homogeneous tetra-cluster catalyst materials Co4-BTA@KB, Ni4-BTA@KB, Cu4-BTA@KB, and Mn4-BTA@KB were prepared by replacing the iron salt with other metal salts.
[0023] Example 2 The 1,2,4,5-phenyltetramine monomer in Example 1 was replaced with the 2,3,6,7,10,11-hexaaminotriphenyl monomer (HATP), and all other steps were the same as in Example 1, to prepare Fe4-HATP@KB.
[0024] Example 3 Synthesis of polymer-based heterogeneous tetra-atom cluster electrocatalytic materials: First, FeCl2 and CoCl2 were dispersed separately in DMF solution to form FeCl2 and CoCl2 DMF solutions. Then, 1,2,4,5-phenyltetramine monomer was added to the FeCl2 DMF solution to form an amino precursor mixture, and 1,10-phenanthroline-2,9-dicarboxaldehyde monomer was added to the CoCl2 DMF solution to form an aldehyde precursor mixture. Ketjen black was uniformly dispersed in DMF. After uniform dispersion, the precursor mixture of the two monomers was added to this mixture, and the reaction was carried out at 120 °C for 3 days using a solvothermal method. After the reaction was completed, filtration and washing were performed to obtain the polymer-based heterogeneous tetra-atom cluster catalyst material Fe2Co2-B / PDA@KB.
[0025] The remaining polymer-based heterogeneous tetra-cluster catalyst materials Fe2Ni2-B / PDA@KB, Co2Ni2-B / PDA@KB, and Co2Fe2-B / PDA@KB employ similar preparation processes, differing only in the combination of metals and monomers.
[0026] Example 4 The 1,2,4,5-phenyltetramine monomer in Example 3 was replaced with the 2,3,6,7,10,11-hexaaminotriphenyl monomer (HATP), and all other steps were the same as in Example 3, to prepare Fe2Co2-H / PDA@KB.
[0027] The preparation process of polymer-based tetra-atom cluster catalyst is shown in the following reaction formulas (Ⅰ)-(Ⅳ), in which the metal atoms can be reasonably replaced according to the catalytic environment.
[0028]
[0029] (I) Preparation process of polymer-based homogeneous tetra-atom cluster catalyst (tetraamino monomer)
[0030] (II) Preparation process of polymer-based heterogeneous tetra-atom cluster catalyst (tetraamino monomer), the positions of M1 and M2 can be replaced
[0031] (III) Preparation process of polymer-based homogeneous tetra-atom cluster catalyst (hexaamino monomer)
[0032] (IV) Preparation process of polymer-based heterogeneous tetra-atom cluster catalyst (hexaamino monomer), the positions of M1 and M2 can be replaced Figure 1 Transmission electron microscopy image of Fe4-BTA@KB. This demonstrates the successful composite of the polymer and Ketjen Black.
[0033] Figure 2 Aberration-corrected transmission electron microscopy (TEM) image of the Fe4-BTA@KB catalyst. Four metal atoms are observed in the designed configuration, and no aggregation of metal atoms was found, demonstrating a uniform atomic distribution.
[0034] Oxygen reduction performance test The oxygen reduction performance of different catalyst materials was tested using a rotating disk electrode. The specific test method was as follows: temperature 25℃; electrolyte used was an oxygen-saturated 0.1 M KOH aqueous solution; working electrode was a 5 mm diameter glassy carbon rotating disk electrode at 1600 rpm; counter electrode was a carbon rod; and reference electrode was a saturated Ag / AgCl electrode. The reference electrode potential was calibrated using a reversible hydrogen electrode. 6 mg of catalyst was weighed and added to 970 μL of ethanol and 30 μL of 5% Nafion solution for ultrasonic dispersion to prepare catalyst ink. 20 μL of the catalyst ink was dropped onto the rotating disk electrode and allowed to air dry. The scan rate for the oxygen reduction test was 10 mV / s. -1 The results of the rotating disk electrode test for the catalyst are shown in [reference needed]. Figure 3-6 See Table 1-3.
[0035] Figure 3 Linear sweep voltammetric curves of polymer-based homogeneous four-atom cluster catalysts (Fe4-BTA@KB, Co4-BTA@KB, Ni4-BTA@KB, Cu4-BTA@KB, Mn4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte.
[0036] Figure 4 Linear sweep voltammetric curves of polymer-based homo / heterogeneous tetra-cluster catalysts (Fe2Co2-B / PDA@KB, Fe4-BTA@KB, Co4-BTA@KB, Fe2Ni2-B / PDA@KB, Co2Ni2-B / PDA@KB, Ni4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte.
[0037] Figure 5 Linear sweep voltammetric curves of polymer-based heterogeneous four-atom cluster catalysts (Fe2Co2-B / PDA@KB, Co2Fe2-B / PDA@KB, Pt / C) in 0.1 M KOH electrolyte (different positions of the metals).
[0038] Figure 6 Linear sweep voltammetry curves of polymer-based homo / heterogeneous tetra-cluster catalysts (Fe2Co2-H / PDA@KB, Fe2Co2-B / PDA@KB, Fe4-HATP@KB, Fe4-BTA@KB, Pt / C) in 0.1 M KOH electrolyte.
[0039] The oxygen reduction performance of catalysts can be significantly affected by controlling the type of metal used. For example, the Fe4-BTA@KB catalyst exhibited an excellent half-wave potential (0.94 V) in the experiment, which was significantly better than that of comparative catalysts such as Co4-BTA@KB, Ni4-BTA@KB, Cu4-BTA@KB, and Mn4-BTA@KB (Table 1). Figure 3 This indicates that the choice of metal species can effectively regulate the adsorption behavior of key intermediates, thereby controlling the overall ORR activity.
[0040] When a heterobimetal is further introduced into the tetra-atom cluster, the half-wave potential of Fe2Co2-B / PDA@KB increases to 0.98V, which is much higher than that of Fe2Ni2-B / PDA@KB and Co2Ni2-B / PDA@KB (Table 2). Figure 4 Meanwhile, the ORR activity of Fe2Co2-B / PDA@KB was also higher than that of Fe4-BTA@KB and Co4-BTA@KB, indicating that by adjusting the metal composition within the tetra-atom cluster, the adsorption / desorption process of the intermediate can be synergistically optimized, thereby obtaining higher catalytic activity.
[0041] Furthermore, altering the arrangement of metals within the heterotetraatomic cluster can further improve the ORR catalytic performance of the material (Table 3). Figure 5 We also found that by changing the amino monomer, Fe2Co2-H / PDA@KB achieved an ultra-high half-wave potential (1.01V), far exceeding that of commercial Pt / C, fully demonstrating its superior ORR catalytic activity (Table 3). Figure 6 ).
[0042] By synthesizing a series of catalysts with different compositions, this study systematically investigated the effects of metal type (homogeneous / heterogeneous) and amino monomer structure on the electronic structure of active sites. The results showed that these factors can effectively regulate the adsorption behavior of key reaction intermediates, thereby enabling them to exhibit differentiated oxygen reduction catalytic performance. These results further validate the high tunability and design reliability of this type of catalyst in terms of both structure and performance.
[0043] Table 1. Performance of polymer-based homogeneous tetra-cluster catalysts
[0044] Table 2. Performance of polymer-based heterogeneous tetra-cluster catalysts
[0045] Table 3. Performance of other polymer-based homo / hetero-tetra-cluster catalysts
[0046] For any points not covered above, existing technologies shall apply.
[0047] 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 of preparing a polymer-based tetraatomic cluster electrocatalyst material, characterized in that, A amino precursor mixture is formed by adding amino small molecule monomers to a DMF solution of metal M1, and an aldehyde precursor mixture is formed by adding aldehyde small molecule monomers to a DMF solution of metal M2. The amino precursor mixture and the aldehyde precursor mixture are added to a DMF solution of a pre-uniformly dispersed carbon substrate, and a polymer-based tetra-atom cluster electrocatalyst material is formed by Schiff base reaction. The amino small molecule monomer is one of 1,2,4,5-phenyltetramine, 2,3,6,7-tetraaminonaphthalene, anthracene-2,3,6,7-tetramine, 4,5,9,10-tetraaminopyrene, and 2,3,6,7,10,11-hexaaminotriphenyl. The aldehyde-based small molecule monomer is 1,10-phenanthroline-2,9-dicarboxaldehyde; M1 and M2 are one or more of Fe, Co, Ni, Cu, and Mn.
2. The production method according to claim 1, wherein M1 and M2 are made of the same metal.
3. The production method according to claim 2, wherein M1 and M2 are Fe or Co.
4. The preparation method according to claim 1, characterized in that, M1 and M2 are different.
5. The preparation method according to claim 4, characterized in that, M1 or M2 is Fe, and M2 or M1 is Co or Ni.
6. The preparation method according to claim 1, characterized in that, The carbon substrate includes one or more of the following: Ketjen black, conductive carbon black, carbon nanotubes, activated carbon, graphene, carbon cloth, carbon fiber, cotton fabric, polyester, nylon, wool, silk, glass fiber cloth, aramid fiber cloth, and polypropylene.
7. The preparation method according to claim 1, characterized in that, The reaction temperature is 100-120 ℃, and the reaction time is 1-5 days.
8. A polymer-based tetra-cluster electrocatalyst material prepared by the preparation method described in any one of claims 1-7.
9. The application of a polymer-based tetra-cluster electrocatalyst material as described in claim 8 in oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, hydrogen oxidation reaction, or carbon dioxide reduction reaction.