In-situ derived noble metal / transition metal alloy catalysts rich in dislocation defects, methods of making and use thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO UNIV OF SCI & TECH
- Filing Date
- 2022-12-29
- Publication Date
- 2026-07-07
AI Technical Summary
Existing precious metal catalysts are expensive, scarce, and have poor durability. Single 3d transition metal catalysts have insufficient reactivity and cannot meet the bifunctional catalytic requirements of HER and OER.
By synthesizing noble metal/3d transition metal alloys under high temperature and short-time thermal shock, nanoparticles rich in dislocation defects are formed. The catalyst structure and active sites are optimized by utilizing electronic interactions and stress-strain induced lattice distortion.
It significantly improves catalytic activity and durability, reduces the amount of precious metals used, achieves excellent electrocatalytic performance for HER and OER, and is suitable for large-scale industrial production.
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Figure CN116288400B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of catalyst material preparation technology, specifically relating to in-situ derived noble metal / transition metal alloy catalysts rich in dislocation defects, their preparation methods and applications. Background Technology
[0002] With the further advancement of industrialization, the shortage of fossil fuels has become a serious social problem. The resulting energy crisis, environmental pollution, and greenhouse effect are major challenges facing the world this century. Therefore, the development and utilization of clean, sustainable, and renewable energy sources are urgently needed to significantly alleviate the consumption and dependence on finite fossil fuels. Hydrogen energy has attracted widespread attention due to its high energy density, cleanliness, and renewability. Water electrolysis is an advanced energy conversion technology used to produce hydrogen, which is crucial for accelerating energy structure adjustment and promoting the development of the hydrogen energy industry.
[0003] Hydrogen production via water electrolysis involves the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Currently, Pt-based noble metal catalysts are the best HER catalysts, but their OER performance is limited. Meanwhile, Ir / Ru-based catalysts only exhibit high catalytic efficiency for the OER process, but their HER performance is limited. Therefore, single-component noble metal-based catalysts generally cannot be used as multifunctional electrocatalysts. However, their high cost and scarcity of resources prevent their large-scale commercial application.
[0004] Furthermore, the high cost, scarcity, and poor durability of single precious metal catalysts severely hinder their large-scale application.
[0005] Furthermore, while 3d transition metal materials are low-cost and abundant, the main challenge in replacing noble metal catalysts with non-noble metals is how to improve the catalyst's reactivity, thereby lowering the catalytic reaction energy barrier and reducing energy consumption. Single 3d transition metals do not show significant catalytic performance; therefore, single-component 3d transition metal-based catalysts are also insufficient to meet the dual-function catalytic requirements of HER and OER.
[0006] In view of the above, this application is hereby submitted. Summary of the Invention
[0007] To address one of the aforementioned technical deficiencies, this application provides an in-situ derived noble metal / transition metal alloy catalyst rich in dislocation defects, its preparation method, and its application.
[0008] First, the noble metal and 3d transition metal in this application exhibit strong electronic interactions, making alloying them a promising application prospect that can simultaneously improve the catalytic activity and durability of the catalyst. Second, introducing foreign 3d transition metal atoms to form an alloy with noble metal atoms can reduce the amount of noble metal used while maintaining the same catalyst mass, thereby directly reducing the catalyst cost. Third, the introduction of the foreign alloy alters the original atomic arrangement of the noble metal, adjusts its coordination number, changes the electronic structure of the noble metal's active sites, and regulates the d-band center of the noble metal, thereby optimizing the adsorption energy of reaction intermediates on the noble metal's active sites and ultimately increasing its catalytic activity.
[0009] It is worth noting that this application innovatively induces significant stress-strain in noble metal / 3d transition metal alloys under high-temperature, short-time thermal shock synthesis conditions. This results in compression of interplanar spacing, leading to severe lattice distortion, and ultimately inducing the formation of numerous crystal dislocation defects in the alloy nanoparticles, causing a significant rearrangement of their original atomic arrangement. This strain-induced high-energy surface structure is more likely to resist surface recombination during catalysis.
[0010] According to a first aspect of the embodiments of this application, a method for preparing a carbon material catalyst for in-situ derived noble metal / transition metal alloys rich in dislocation defects is provided, comprising:
[0011] COF matrix preparation: Covalent organic framework (COF) matrix was prepared using Schiff base reaction;
[0012] Preparation of COF precursors anchored to metal ions: The COF matrix obtained was thoroughly mixed with noble metal salts, transition metal salts, and zinc nitrate, and then dried to obtain COF precursors anchored to metal ions.
[0013] Noble metal atoms and transition metal atoms diffuse, crystallize, and grow in situ on a COF matrix to form nanoparticles: the COF precursor anchored with metal ions is rapidly heated to a preset temperature using Joule heating, then held at the preset temperature for a preset time, and finally rapidly cooled; the Joule heating process is repeated a preset number of times.
[0014] Nanoparticle carbonization treatment: The above nanoparticles can be carbonized at high temperature to obtain carbon material catalysts with in-situ derived noble metal / transition metal alloys rich in dislocation defects.
[0015] Preferably, the noble metal salt is at least one of iridium salt, platinum salt, or palladium salt;
[0016] The transition metal salt is at least one of iron salt, nickel salt, cobalt salt, and manganese salt.
[0017] Preferably, noble metal atoms and transition metal atoms diffuse, crystallize, and grow in situ on a COF matrix to form nanoparticles; specifically:
[0018] The material is rapidly heated to 1500-2500℃ within 3-8 seconds using Joule heating; then held at this temperature for 10-40 seconds; and finally rapidly cooled to room temperature within 1-6 seconds. The above operation is repeated 1-4 times to obtain in-situ derived noble metal / transition metal alloy nanoparticles rich in dislocation defects from the COF matrix.
[0019] Preferably, the nanoparticles are carbonized; specifically:
[0020] The nanoparticles were calcined at 900℃ for 2-3 hours in an Ar atmosphere in a tube furnace to completely remove organic impurities and ensure thorough and uniform carbonization. This yielded macroporous carbon materials derived from COFs, in situ grown from alloy nanoparticles of metal atoms and transition metal atoms.
[0021] The preferred method for preparing COF precursors anchored to metal ions is as follows:
[0022] The obtained COF matrix was mixed with aqueous solutions of iridium chloride, manganese chloride and zinc acetate in acetonitrile solution, stirred thoroughly for 2 h, centrifuged and washed, and then vacuum dried at 80 °C for 12 h to obtain COF precursors anchored to metal ions.
[0023] Preferably, the preparation of the COFs matrix is as follows:
[0024] The COF matrix was obtained by dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in anhydrous ethanol using a solution method, stirring thoroughly, and then centrifuging and vacuum drying.
[0025] According to the second aspect provided in the embodiments of this application, an in-situ derived carbon material catalyst rich in dislocation defects of noble metal / transition metal alloy is provided, which is prepared by the above preparation method;
[0026] The carbon material catalyst is rich in noble metal / transition metal alloy particles with dislocation defects; wherein the mass fraction of the noble metal / transition metal alloy is 3-15 wt%, the size of the noble metal / transition metal alloy nanoparticles is 5-30 nm, and the macropore size on the carbon matrix is 100-500 nm.
[0027] Preferably, the noble metal / transition metal alloy particles are IrMn alloy nanoparticles; the IrMn alloy has internal lattice compression, reduced interplanar spacing and severe lattice distortion; a large number of dislocation defects and lattice misalignments are formed in the IrMn alloy nanoparticles.
[0028] According to a third aspect provided in the embodiments of this application, a carbon material catalyst prepared by the above preparation method or the above carbon material catalyst is provided for use in water electrolysis.
[0029] The beneficial effects of this application are:
[0030] 1. This application innovatively utilizes the unstable thermal shock of Joule heating to rapidly and in-situ generate carbon catalysts rich in dislocation defects, forming noble metal / transition metal alloys. Under Joule heating conditions, the adsorption effect between the two promotes the formation of the noble metal / transition metal alloy. However, the kinetic diffusion rates of noble metal / transition metal atoms in the carbon matrix differ, and both have relatively large atomic radii. Therefore, the formed noble metal / transition metal alloy nanoparticles contain a large number of dislocation defects and lattice distortions, effectively optimizing the electronic structure of the alloy nanoparticles, significantly regulating the metal d-band centers, and the adsorption characteristics of reaction intermediates. Thus, it can provide rich catalytic activity for HER and OER.
[0031] 2. The heteroatom-doped macroporous carbon / alloy composite catalyst prepared in this application possesses advantages such as abundant dislocation defects, high density of active sites, large tunability of pore size, and synergistic effects among multiple active components. Furthermore, the COFs-derived macroporous carbon matrix supported on metal alloys prepared by this method has a specific surface area as high as 1260 m² / g, which provides abundant anchoring sites for the in-situ loading of alloy nanoparticles and ensures their full exposure, all of which are beneficial for improving catalytic kinetics.
[0032] 3. In the preparation process of this application, rapid thermal shocks were repeatedly employed. Due to the rapid thermal shocks and the differences in their atomic radii, the noble / transition metals underwent stress-strain effects within their internal lattice during the formation of the IrMn alloy. This caused atomic lattice misalignment in the IrMn alloy, further leading to structural reorganization of the catalyst atoms, inducing lattice compression within the IrMn alloy, resulting in a reduction in interplanar spacing and thus severe lattice distortion. This lattice distortion ultimately leads to the formation of numerous dislocation defects and lattice misalignments within the IrMn alloy nanoparticles. The high-energy surface structure induced by this method is more likely to suppress catalyst surface oxidation and structural reconstruction during catalysis. This results in better catalytic performance and stability of the catalyst.
[0033] 4. In this application, the explosive effect of zinc acetate during Joule heating causes the porous carbon matrix derived from COFs to produce a macroporous structure, which is beneficial to increase the specific surface area, increase metal loading sites, expose more reactive sites, enhance electrolyte wetting effect, and improve charge-mass transport efficiency.
[0034] 5. The synthesis method of this application is universal. By changing the types of noble metal salts and 3d transition metal salts, the obtained catalyst materials all exhibit excellent electrocatalytic performance. The catalysts demonstrate excellent electrocatalytic performance under both alkaline (1.0 MkOH) and acidic (0.5 Mh₂SO₄) conditions. HER performance testing shows that it achieves nearly the same overpotential as commercial platinum-carbon catalysts, but with a smaller Tafel slope. OER performance testing at a current density of 10 mA / cm² also shows excellent performance. 2 At this time, the overpotential is much lower than that of commercial ruthenium dioxide catalysts, and this bifunctional catalyst has good application prospects in alkaline water electrolysis.
[0035] 6. The synthesis method of this application is simple, has abundant yield, good reproducibility, and uses inexpensive chemicals with readily available raw materials, making it suitable for large-scale industrial production. Attached Figure Description
[0036] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:
[0037] Figure 1 Here is a SEM image of the IrMn-NC alloy catalyst material prepared in this application;
[0038] Figure 2 Aberration-corrected electron microscopy image of the IrMn-NC alloy catalyst material prepared in this application;
[0039] Figure 3 TEM image of the IrMn-NC alloy catalyst material prepared in this application;
[0040] Figure 4 The image shows the electrocatalytic hydrogen evolution (HER) performance of the IrMn-NC alloy catalyst material prepared in this application under acidic conditions.
[0041] Figure 5 The figure shows the electrocatalytic oxygen evolution (OER) performance of the IrMn-NC alloy catalyst material prepared in this application under acidic conditions.
[0042] Figure 6 The electrolysis performance of the IrMn-NC alloy catalyst material prepared in this application under acidic conditions is shown in the figure. Detailed Implementation
[0043] To make the technical solutions and advantages of the embodiments of this application clearer, the exemplary embodiments of this application will be described in further detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not an exhaustive list of all embodiments. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.
[0044] Embodiments of this application provide a method for preparing a carbon material catalyst derived in situ from a noble metal / transition metal alloy rich in dislocation defects, comprising the following steps:
[0045] (S1) Preparation of COF matrix: Covalent organic framework (COF) matrix was prepared by Schiff base reaction;
[0046] (S2) Preparation of COF precursors anchored to metal ions: The COF matrix obtained is thoroughly mixed with noble metal salt, transition metal salt and zinc nitrate and dried to obtain COF precursors anchored to metal ions.
[0047] (S3) Noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on the COFs matrix to form nanoparticles: The COFs precursor anchored with metal ions is rapidly heated to a preset temperature using Joule heating, then held at the preset temperature for a preset time, and finally rapidly cooled; the Joule heating process is repeated a preset number of times.
[0048] (S4) Carbonization of nanoparticles: The above nanoparticles can be carbonized at high temperature to obtain carbon material catalysts with in-situ derived noble metal / transition metal alloys rich in dislocation defects.
[0049] The embodiments of this application provide a method for preparing a carbon material catalyst with in-situ derived noble metal / transition metal alloy rich in dislocation defects, wherein the noble metal salt is at least one of iridium salt, platinum salt or palladium salt; and the transition metal salt is at least one of iron salt, nickel salt, cobalt salt or manganese salt.
[0050] This application provides a method for preparing a carbon material catalyst with in-situ derived noble metal / transition metal alloys rich in dislocation defects. Noble metal atoms and transition metal atoms diffuse, crystallize, and grow in-situ on a COF matrix to form nanoparticles. Specifically:
[0051] The material is rapidly heated to 1500-2500℃ within 3-8 seconds using Joule heating; then held at this temperature for 10-40 seconds; and finally rapidly cooled to room temperature within 1-6 seconds. The above operation is repeated 1-4 times to obtain in-situ derived noble metal / transition metal alloy nanoparticles rich in dislocation defects from the COF matrix.
[0052] This application provides a method for preparing carbon material catalysts of noble metal / transition metal alloys rich in dislocation defects in situ, involving nanoparticle carbonization treatment; specifically:
[0053] The nanoparticles were calcined at 900℃ for 2-3 hours in an Ar atmosphere in a tube furnace to completely remove organic impurities and ensure thorough and uniform carbonization. This yielded macroporous carbon materials derived from COFs, in situ grown from alloy nanoparticles of metal atoms and transition metal atoms.
[0054] This application provides a method for preparing carbon material catalysts of noble metal / transition metal alloys rich in dislocation defects in situ, specifically the preparation of COFs precursors anchored to metal ions:
[0055] The obtained COF matrix was mixed with aqueous solutions of iridium chloride, manganese chloride and zinc acetate in acetonitrile solution, stirred thoroughly for 2 h, centrifuged and washed, and then vacuum dried at 80 °C for 12 h to obtain COF precursors anchored to metal ions.
[0056] This application provides a method for preparing carbon material catalysts derived in situ from noble metal / transition metal alloys rich in dislocation defects. The specific preparation of the COF matrix is as follows:
[0057] The COF matrix was obtained by dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in anhydrous ethanol using a solution method, stirring thoroughly, and then centrifuging and vacuum drying.
[0058] This application provides a method for preparing a carbon material catalyst derived in situ from a noble metal / transition metal alloy rich in dislocation defects, comprising the following specific steps:
[0059] (1) Terephthalaldehyde, p-phenylenediamine and glacial acetic acid were dissolved in anhydrous ethanol by solution method, stirred thoroughly, and then centrifuged and vacuum dried to obtain COFs matrix.
[0060] (2) The obtained COF matrix was mixed with aqueous solutions of iridium chloride, manganese chloride and zinc acetate in acetonitrile solution, stirred thoroughly for 2 h, centrifuged and washed, and then vacuum dried at 80 °C for 12 h to obtain the metal-loaded COF precursor.
[0061] (3) High-temperature calcination preparation of IrMn alloy: The COFs precursor with loaded metal obtained in step (2) is subjected to Joule heating. This process utilizes the unstable thermal shock of Joule heating to rapidly raise the carbon material to 1500-2500℃ in about 3-8s, then hold it at this temperature for 10-40s; finally, it is rapidly cooled to 25℃ in 1-6s, and the above operation is repeated 1-4 times. In this way, noble metals and 3d transition metals are grown in situ on the macroporous carbon matrix derived from COFs to form IrMn alloy nanoparticles rich in dislocation defects. Specifically, zinc acetate undergoes a bursting effect at the temperature of rapid thermal shock, which generates a large number of macropores in the COFs-derived carbon matrix, which is beneficial to increase the specific surface area, increase the metal loading sites, expose more reactive sites, enhance electrolyte wetting characteristics, and improve charge transport efficiency.
[0062] (4) Calcination at 900℃ for 2-3 hours under Ar atmosphere to obtain the final IrMn alloy: The material obtained by Joule heating is calcined at 900℃ for 2 hours to fully carbonize it and remove impurities caused by incomplete carbonization. The final IrMn-NC alloy catalyst material is obtained; The carbon material with IrMn alloy nanoparticles loaded by Joule heating is then calcined at 900℃ for 2-3 hours in Ar atmosphere in a tube furnace to completely remove organic impurities from the carbon material and to ensure that it is fully and uniformly carbonized. In this way, an electrocatalyst with IrMn alloy nanoparticles grown in situ and loaded on a COFs-derived macroporous carbon matrix is obtained, and the COFs-derived macroporous carbon matrix is doped with abundant N, Ir, and Mn heteroatoms.
[0063] During implementation, due to the electronic interactions between Ir and Mn atoms, the adsorption effect between them under Joule heating promotes the formation of IrMn alloys. However, the kinetic diffusion rates of Ir and Mn atoms in the carbon matrix differ, and coupled with their large atomic radii, the resulting IrMn alloy nanoparticles contain numerous dislocation defects and lattice distortions. This effectively optimizes the electronic structure of the alloy nanoparticles, significantly modulates the metal d-band centers, and enhances the adsorption characteristics of reaction intermediates, thus providing abundant catalytic activity for HER and OER. Simultaneously, rapid and unstable thermal shock causes zinc nitrate to volatilize rapidly, and the intense explosive effect creates abundant macroporous structures on the carbon matrix, which significantly increases the specific surface area and fully exposes active sites.
[0064] Embodiments of this application provide the application of an in-situ derived carbon material catalyst rich in dislocation defects, a noble metal / transition metal alloy, in water electrolysis.
[0065] The IrMn-NC alloy catalyst material prepared in this application was analyzed by SEM, TEM and spherical aberration electron microscopy.
[0066] Figure 1 The image shows a SEM image of the IrMn-NC alloy catalyst material prepared in this application. It can be seen from the image that a macroporous carbon matrix was formed by COFs loaded with IrMn alloy nanoparticles. The macropore size on the carbon matrix is 100-500 nm.
[0067] Figure 2 The image shows a spherical aberration electron microscope (SEM) image of the IrMn-NC alloy catalyst material prepared in this application. The image shows that the IrMn alloy is uniformly distributed on the carbon matrix. The size of the IrMn alloy nanoparticles ranges from 5 to 30 nm.
[0068] Figure 3 The image shows a TEM image of the IrMn-NC alloy catalyst material prepared in this application; it can be seen from the image that there are abundant dislocation defects and lattice distortions in the IrMn nano-alloy particles.
[0069] Figure 4 The graph shows the electrocatalytic hydrogen evolution (HER) performance of the IrMn-NC alloy catalyst material prepared in this application under acidic conditions. It can be seen from the graph that under acidic conditions, only a 25 mV overpotential is required to reach 10 mA / cm². 2 Current density.
[0070] Figure 5 The electrocatalytic oxygen evolution (OER) performance of the IrMn-NC alloy catalyst material prepared for this application under acidic conditions is shown in the figure: Under acidic conditions, an OER of 10 mA / cm² is achieved with an overpotential of only 310 mV. 2 Current density.
[0071] Figure 6 The electrolysis performance of the IrMn-NC alloy catalyst material prepared for this application under acidic conditions is shown in the figure: 10 mA / cm² can be achieved in acidic total hydrolysis with only 1.47 V. 2 Current density.
[0072] Heteroatom-doped macroporous carbon / alloy composite catalysts possess advantages such as abundant dislocation defects, high density of active sites, large pore size tunability, and synergistic effects among multiple active components. Furthermore, the COFs-derived macroporous carbon matrix supported on metal alloys prepared by this method provides abundant anchoring sites for the in-situ loading of alloy nanoparticles and ensures their full exposure, all of which contribute to improved catalytic kinetics.
[0073] The mass fraction of the IrMn alloy was determined to be 3-15 wt% using inductively coupled plasma optical emission spectrometry (ICP-OES), with IrMn alloy nanoparticles ranging in size from 5-30 nm. The macropore size on the carbon matrix was 100-500 nm. N2 adsorption-desorption curves revealed a specific surface area as high as 1260 m² / s.2 / g.
[0074] Based on the above, this application innovatively utilizes rapid, unstable thermal shock and dislocation effects caused by differences in atomic radii to induce lattice distortion, thereby altering the interplanar spacing and triggering a strain effect. This change leads to differential arrangement of the original atoms, forming abundant dislocation defects in the alloy nanoparticles, which is the key reason for its excellent HER and OER catalytic activity. Simultaneously, the high-energy surface structure dominated by dislocation defects is more likely to resist surface reconstruction and matrix oxidation during catalysis. This results in bimetallic IrMn alloy catalysts exhibiting excellent catalytic performance and durability.
[0075] Although preferred embodiments of this application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this application.
[0076] Obviously, those skilled in the art can make various modifications and variations to this application without departing from the spirit and scope of this application. Therefore, if such modifications and variations fall within the scope of the claims of this application and their equivalents, this application also intends to include such modifications and variations.
Claims
1. A method for preparing a carbon material catalyst derived in situ from a noble metal / transition metal alloy rich in dislocation defects, characterized in that, COF matrix preparation: Covalent organic framework (COF) matrix was prepared using Schiff base reaction; Preparation of COF precursors anchored to metal ions: The COF matrix obtained was thoroughly mixed with noble metal salts, transition metal salts, and zinc nitrate, and then dried to obtain COF precursors anchored to metal ions. Noble metal atoms and transition metal atoms diffuse, crystallize, and grow in situ on a COF matrix to form nanoparticles: the COF precursor anchored with metal ions is rapidly heated to a preset temperature using Joule heating, then held at the preset temperature for a preset time, and finally rapidly cooled; the Joule heating process is repeated a preset number of times. Nanoparticle carbonization treatment: The above nanoparticles can be carbonized at high temperature to obtain carbon material catalysts with in-situ derived noble metal / transition metal alloys rich in dislocation defects.
2. The preparation method according to claim 1, characterized in that, The noble metal salt is at least one of iridium salt, platinum salt, or palladium salt; The transition metal salt is at least one of iron salt, nickel salt, cobalt salt, and manganese salt.
3. The preparation method according to claim 1, characterized in that, Noble metal atoms and transition metal atoms diffuse, crystallize, and grow in situ on a COF matrix to form nanoparticles; specifically: The material is rapidly heated to 1500-2500℃ within 3-8 seconds using Joule heating; then held at this temperature for 10-40 seconds; and finally rapidly cooled to room temperature within 1-6 seconds. The above operation is repeated 1-4 times to obtain in-situ derived noble metal / transition metal alloy nanoparticles rich in dislocation defects from the COF matrix.
4. The preparation method according to claim 1, characterized in that, Nanoparticle carbonization treatment; specifically: The nanoparticles were calcined at 900℃ for 2-3 hours in an Ar atmosphere in a tube furnace to completely remove organic impurities and ensure thorough and uniform carbonization. This yielded macroporous carbon materials derived from COFs, in situ grown from alloy nanoparticles of metal atoms and transition metal atoms.
5. The preparation method according to claim 1, characterized in that, The preparation of COF precursors anchored to metal ions is as follows: The obtained COF matrix was mixed with aqueous solutions of iridium chloride, manganese chloride and zinc acetate in acetonitrile solution, stirred thoroughly for 2 h, centrifuged and washed, and then vacuum dried at 80 °C for 12 h to obtain COF precursors anchored to metal ions.
6. The preparation method according to claim 1, characterized in that, The specific preparation of the COF matrix is as follows: The COF matrix was obtained by dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in anhydrous ethanol using a solution method, stirring thoroughly, and then centrifuging and vacuum drying.
7. A carbon material catalyst for in-situ derived noble metal / transition metal alloys rich in dislocation defects, characterized in that, Prepared using the preparation method described in any one of claims 1-6; The carbon catalyst is rich in noble metal / transition metal alloy particles with dislocation defects; wherein the mass fraction of the noble metal / transition metal alloy is 3-15 wt%, the size of the noble metal / transition metal alloy nanoparticles is 5-30 nm, and the macropore size on the carbon matrix is 100-500 nm; the COFs-derived macroporous carbon matrix in the carbon catalyst has a specific surface area as high as 1260 m². 2 / g.
8. The carbon material catalyst as described in claim 7, characterized in that, The noble metal / transition metal alloy particles are IrMn alloy nanoparticles; the IrMn alloy has internal lattice compression, reduced interplanar spacing and severe lattice distortion; a large number of dislocation defects and lattice misalignments are formed in the IrMn alloy nanoparticles.
9. The carbon material catalyst prepared by any one of claims 1 to 6 or the carbon material catalyst prepared by any one of claims 7 to 8, in the application of water electrolysis.