CN116288400A - Noble metal/transition metal alloy catalyst rich in dislocation defects and preparation method and application thereof - Google Patents
Noble metal/transition metal alloy catalyst rich in dislocation defects and preparation method and application thereof Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The application provides a preparation method of a carbon material catalyst for in-situ derivatization of a noble metal/transition metal alloy rich in dislocation defects, which comprises the following steps: preparing a covalent organic framework COFs matrix by utilizing Schiff base reaction; fully mixing the obtained COFs matrix with noble metal salt, transition metal salt and zinc nitrate, and drying to obtain a COFs precursor of the anchoring metal ion; heating the COFs precursor of the anchored metal ion to a preset temperature by Joule heating, preserving heat for a preset time at the preset temperature, and cooling by rapid cooling; repeating the Joule heating process for the preset times; under the high-temperature short-time thermal shock synthesis condition, obvious stress strain is innovatively generated in the noble metal/3 d transition metal alloy, so that serious lattice distortion is caused by the compression of the interplanar spacing, and a large number of crystal dislocation defects are finally induced and formed in the alloy nano particles, so that the original atomic arrangement mode of the alloy nano particles is obviously rearranged.
Description
Technical Field
The application belongs to the technical field of catalyst material preparation, and particularly relates to an in-situ derived noble metal/transition metal alloy catalyst rich in dislocation defects, and a preparation method and application thereof.
Background
With further improvement of the degree of social industrialization, shortage of fossil energy has become a serious social problem. The resulting energy crisis, environmental pollution and greenhouse effect problems are major challenges facing the world in this century. Therefore, there is an urgent need to develop and utilize clean, sustainable, renewable clean energy sources to greatly mitigate the consumption and reliance on limited fossil energy sources. Hydrogen energy is receiving attention because of its high energy density, green cleaning and renewable advantages. The water electrolysis is an advanced energy conversion technology for producing hydrogen energy, and has key significance for accelerating energy structure adjustment and promoting the development of the hydrogen energy industry.
Electrolytic water hydrogen production comprises Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), and Pt-based noble metals are currently the most excellent HER catalysts, but OER performance is limited. Meanwhile, ir/Ru-based catalysts have only high catalytic efficiency for OER processes, but the HER performance is limited. Therefore, single component noble metal-based catalysts are generally not useful as multifunctional electrocatalysts. But cannot be used on a large scale due to its high cost and resource starvation.
In addition, the single noble metal catalyst is severely hampered in its large-scale application due to its high cost, scarcity, and poor durability.
Again, the main problem faced by using 3d transition metal materials, albeit at low cost and rich levels, to replace noble metal catalysts with non-noble metals is how to increase the reactivity of the catalysts, thereby reducing the catalytic reaction energy barrier and reducing the energy consumption. The single 3d transition metal has no remarkable effect on the catalytic performance, so that the single-component 3d transition metal-based catalyst is also difficult to meet the requirements of HER and OER dual-function catalysis.
In view of this, the present application is specifically proposed.
Disclosure of Invention
In order to solve one of the technical defects, the embodiment of the application provides a noble metal/transition metal alloy catalyst rich in dislocation defects, and a preparation method and application thereof.
Firstly, the noble metal and the 3d transition metal have strong electronic interaction, and alloying the noble metal and the 3d transition metal has excellent application prospect, so that the catalytic activity and the durability of the catalyst can be improved simultaneously. Secondly, the external 3d transition metal atoms and noble metal atoms are introduced to form an alloy, so that the use amount of noble metal can be reduced on the premise of keeping the same catalyst quality, and the cost of the catalyst is directly reduced. Thirdly, the introduction of the external alloy changes the atomic arrangement of the original noble metal, adjusts the coordination number of the noble metal, changes the electronic structure of the noble metal active site, regulates and controls the d-band center of the noble metal, further optimizes the adsorption energy of the reaction intermediate product on the noble metal active site, and finally increases the catalytic activity of the reaction intermediate product.
It is worth to say that, the noble metal/3 d transition metal alloy innovatively generates obvious stress strain under the high-temperature short-time thermal shock synthesis condition, so that the compression of the interplanar spacing occurs to cause serious lattice distortion, and a large number of crystal dislocation defects are finally induced to form in the alloy nano particles, so that the original atomic arrangement mode of the alloy nano particles is obviously rearranged. Such strain-induced high-energy surface structures are more likely to resist surface recombination during catalysis.
According to a first aspect of embodiments of the present application, there is provided a method for preparing a carbon material catalyst for in situ derivatizing a noble metal/transition metal alloy rich in dislocation defects, comprising:
COFs matrix preparation: preparing a covalent organic framework COFs matrix by utilizing Schiff base reaction;
preparation of COFs precursor anchoring metal ions: fully mixing the obtained COFs matrix with noble metal salt, transition metal salt and zinc nitrate, and drying to obtain a COFs precursor of the anchoring metal ion;
noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on COFs substrates to form nanoparticles: heating the COFs precursor of the anchored metal ion to a preset temperature by Joule heating, preserving heat for a preset time at the preset temperature, and cooling by rapid cooling; repeating the Joule heating process for the preset times;
carbonizing nano particles: and carrying out high-temperature carbonization treatment on the nano particles to obtain the carbon material catalyst of the noble metal/transition metal alloy which is derived in situ and is rich in dislocation defects.
Preferably, 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 ferric salt, nickel salt, cobalt salt and manganese salt.
Preferably, noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on COFs substrates to form nanoparticles; the method comprises the following steps:
heating the material to 1500-2500 deg.c in joule heating for 3-8 s; then preserving heat at the temperature for 10-40s; finally, rapidly cooling to room temperature within 1-6 s; repeating the above operation for 1-4 times; and obtaining the noble metal/transition metal alloy nano particles which are derived from the COFs matrix in situ and are rich in dislocation defects.
Preferably, the nanoparticles are carbonized; the method comprises the following steps:
calcining at 900 ℃ for 2-3 hours in a tubular furnace under Ar atmosphere to thoroughly remove the organic impurities of the nano particles, so that the nano particles are fully carbonized and completely uniform; the macroporous carbon material derived from COFs is obtained by in-situ growth of metal atom and transition metal atom alloy nano particles.
Preferably, the preparation of the COFs precursor anchoring the metal ion is specifically:
mixing the obtained COFs matrix with iridium chloride, manganese chloride and zinc acetate aqueous solution in acetonitrile solution, fully stirring for 2 hours, centrifugally cleaning, and then vacuum drying at 80 ℃ for 12 hours; the obtained COFs precursor for anchoring metal ions.
Preferably, the COFs matrix is prepared specifically by:
dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in absolute ethyl alcohol by a solution method, fully and uniformly stirring, and then carrying out centrifugal vacuum drying to obtain the COFs matrix.
According to a second aspect provided by embodiments of the present application, there is provided a carbon material catalyst for in-situ derivatizing a noble metal/transition metal alloy rich in dislocation defects, prepared by the preparation method described above;
the carbon material catalyst is rich in precious metal/transition metal alloy particles with dislocation defects; wherein the mass fraction of the noble metal/transition metal alloy is 3-15wt%, the size of the noble metal/transition metal alloy nano particles is 5-30nm, and the size of macropores on the carbon matrix is 100-500nm.
Preferably, the noble metal/transition metal alloy particles are IrMn alloy nanoparticles; the internal lattice of the IrMn alloy is compressed, the interplanar spacing is reduced, and serious lattice distortion is generated; a number of dislocation defects and lattice dislocation rows are formed in the IrMn alloy nanoparticles.
According to a third aspect provided by the embodiments of the present application, there is provided a carbon material catalyst prepared by the above preparation method or an application of the carbon material catalyst in water electrolysis.
The beneficial effects of this application:
1. the present application innovatively utilizes the unstable thermal shock of joule heating to rapidly derive in situ the carbon material catalyst of noble metal/transition metal alloy rich in dislocation defects; the adsorption effect between the two under joule heating promotes the formation of noble/transition metal alloys. However, the noble metal/transition metal atoms have different dynamic diffusion speeds in the carbon matrix and have larger atomic radii, so that a large number of dislocation defects and lattice distortions exist in the formed noble metal/transition metal alloy nanoparticles, the electronic structure of the alloy nanoparticles is effectively optimized, the metal d-band center and the adsorption characteristic to reaction intermediate products are obviously regulated and controlled, and therefore, abundant catalytic activities can be provided for HERs and OERs.
2. The heteroatom doped macroporous carbon/alloy composite catalyst prepared by the application has the advantages of abundant dislocation defects, high-density active sites, large pore diameter adjustability, synergistic effect among multiple active components and the like. Meanwhile, the specific surface area of the COFs-derived macroporous carbon matrix loaded with the metal alloy prepared by the method is up to 1260m < 2 >/g, so that abundant anchoring sites are provided for in-situ loading of the alloy nanoparticles, and sufficient exposure of the alloy nanoparticles is ensured, which is beneficial to improving catalytic dynamics.
3. In the preparation process of the present application, rapid thermal shock is adopted for many times, and the noble metal/transition metal has a stress strain effect in the crystal lattice at the same time as the IrMn alloy is formed and inside due to the rapid thermal shock and the difference of different atomic radii. The atomic lattices of the IrMn alloy are subjected to dislocation, further structural recombination of the catalyst atomic arrangement is caused, internal lattice compression of the IrMn alloy is induced, and the inter-plane distance is reduced, so that serious lattice distortion is generated. This lattice distortion ultimately results in the formation of a large number of dislocation defects and lattice dislocation rows in the IrMn alloy nanoparticles. The high-energy surface structure induced by the method is more likely to inhibit the oxidation and the structural reconstruction of the catalyst surface in the catalysis process. Thus, the catalyst has better catalytic performance and stability.
4. In the application, the porous carbon matrix derived from the COFs generates a macroporous structure due to the blasting effect brought by the zinc acetate in the Joule heating process, so that the specific surface area is increased; the metal loading sites are increased, more reactive sites are exposed, the electrolyte infiltration effect is enhanced, and the charge transport efficiency is improved.
5. The synthesis method has universality, and the obtained catalyst material has excellent electrocatalytic performance by changing the types of noble metal salt and 3d transition metal salt; the catalyst was either basic 1.0MKOH or acidic 0.5MH 2 SO 4 Under the condition, the catalyst shows excellent electrocatalytic performance. Through HER performance test, the commercial platinum carbon catalyst can reach nearly the same overpotential and smaller Tafil slope, and through OER performance test, the current density is 10mA/cm 2 At the time, the overpotential is far lower than that of commercial ruthenium dioxide catalyst, and the dual-function catalyst is used in alkaline electrolyzed waterHas better application prospect.
6. The synthesis method is simple, the yield is rich, the repeatability is good, the price of the used chemicals is low, the raw materials are easy to obtain, and the method is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application. In the drawings:
FIG. 1 is an SEM image of an IrMn-N-C alloy catalyst material prepared according to the present application;
FIG. 2 is a spherical aberration electron microscope image of the IrMn-N-C alloy catalyst material prepared in the present application;
FIG. 3 is a TEM image of the IrMn-N-C alloy catalyst material prepared herein;
FIG. 4 is a graph of the electrocatalytic Hydrogen Evolution (HER) performance of the IrMn-N-C alloy catalyst material prepared herein under acidic conditions;
FIG. 5 is a graph showing the electrocatalytic Oxygen Evolution (OER) performance of the IrMn-N-C alloy catalyst material prepared herein under acidic conditions;
FIG. 6 is a graph showing the performance of the IrMn-N-C alloy catalyst material prepared in accordance with the present application in water electrolysis under acidic conditions.
Detailed Description
In order to make the technical solutions and advantages of the embodiments of the present application more apparent, the following detailed description of exemplary embodiments of the present application is given with reference to the accompanying drawings, and it is apparent that the described embodiments are only some of the embodiments of the present application and not exhaustive of all the embodiments. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatizing a noble metal/transition metal alloy rich in dislocation defects, which comprises the following steps:
(S1) preparation of a COFs matrix: preparing a covalent organic framework COFs matrix by utilizing Schiff base reaction;
(S2) preparation of metal ion anchored COFs precursor: fully mixing the obtained COFs matrix with noble metal salt, transition metal salt and zinc nitrate, and drying to obtain a COFs precursor of the anchoring metal ion;
(S3) noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on COFs substrates to form nanoparticles: heating the COFs precursor of the anchored metal ion to a preset temperature by Joule heating, preserving heat for a preset time at the preset temperature, and cooling by rapid cooling; repeating the Joule heating process for the preset times;
(S4) carbonizing the nano particles: and carrying out high-temperature carbonization treatment on the nano particles to obtain the carbon material catalyst of the noble metal/transition metal alloy which is derived in situ and is rich in dislocation defects.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatizing a 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; the transition metal salt is at least one of ferric salt, nickel salt, cobalt salt and manganese salt.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatization of noble metal/transition metal alloy rich in dislocation defects, wherein noble metal atoms and transition metal atoms are diffused, crystallized and grown in situ on a COFs matrix to form nano particles; the method comprises the following steps:
heating the material to 1500-2500 deg.c in joule heating for 3-8 s; then preserving heat at the temperature for 10-40s; finally, rapidly cooling to room temperature within 1-6 s; repeating the above operation for 1-4 times; and obtaining the noble metal/transition metal alloy nano particles which are derived from the COFs matrix in situ and are rich in dislocation defects.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatizing noble metal/transition metal alloy rich in dislocation defects, and nano-particle carbonization treatment; the method comprises the following steps:
calcining at 900 ℃ for 2-3 hours in a tubular furnace under Ar atmosphere to thoroughly remove the organic impurities of the nano particles, so that the nano particles are fully carbonized and completely uniform; the macroporous carbon material derived from COFs is obtained by in-situ growth of metal atom and transition metal atom alloy nano particles.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatization of a noble metal/transition metal alloy rich in dislocation defects, which comprises the following steps of:
mixing the obtained COFs matrix with iridium chloride, manganese chloride and zinc acetate aqueous solution in acetonitrile solution, fully stirring for 2 hours, centrifugally cleaning, and then vacuum drying at 80 ℃ for 12 hours; the obtained COFs precursor for anchoring metal ions.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatization of noble metal/transition metal alloy rich in dislocation defects, wherein the preparation of a COFs matrix specifically comprises the following steps:
dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in absolute ethyl alcohol by a solution method, fully and uniformly stirring, and then carrying out centrifugal vacuum drying to obtain the COFs matrix.
The embodiment of the application provides a preparation method of a carbon material catalyst for in-situ derivatizing a noble metal/transition metal alloy rich in dislocation defects, which comprises the following specific steps:
(1) Dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in absolute ethyl alcohol by a solution method, fully and uniformly stirring, and then carrying out centrifugal vacuum drying to obtain the COFs matrix.
(2) Mixing the obtained COFs matrix with iridium chloride, manganese chloride and zinc acetate aqueous solution in acetonitrile solution, fully stirring for 2 hours, centrifugally cleaning, and then vacuum drying at 80 ℃ for 12 hours; to obtain the metal-loaded COFs precursor.
(3) High-temperature calcination is carried out to prepare IrMn alloy: and (3) carrying out joule heating on the metal-loaded COFs precursor obtained in the step (2). The process is to rapidly heat the carbon material to 1500-2500 ℃ for about 3-8s by using the unstable thermal shock of Joule heating, and then keep the temperature for 10-40s; and finally, rapidly cooling to 25 ℃ for 1-6s, and repeating the above operation for 1-4 times. Thus, noble metal and 3d transition metal grow in situ on the macroporous carbon matrix derived from COFs to form IrMn alloy nano particles rich in dislocation defects. Specifically, zinc acetate produces blasting effect at the temperature of rapid thermal shock, so that a large number of macroporous pores are produced in the COFs-derived carbon matrix, which is beneficial to increasing the specific surface area, increasing metal loading sites, exposing more reactive sites, enhancing the electrolyte infiltration characteristic and improving the charge mass transmission efficiency.
(4) Calcining for 2-3h at 900 ℃ in Ar atmosphere to obtain the final IrMn alloy: the material obtained by joule heating was calcined at 900 ℃ for 2 hours to sufficiently carbonize it, thereby removing impurities in the material due to incomplete carbonization. Finally obtaining the IrMn-N-C alloy catalyst material; the IrMn alloy nanoparticle-loaded carbon material obtained by Joule heating is calcined at 900 ℃ for 2-3 hours in a tubular furnace under Ar atmosphere, so that organic impurities of the carbon material are thoroughly removed, and the carbon material is fully carbonized and completely uniform. Thus, the IrMn alloy nano-particles grow and load on the COFs-derived macroporous carbon matrix electrocatalyst in situ, and the COFs-derived macroporous carbon matrix is doped with rich N, ir and Mn heteroatoms.
In practice, due to the certain electron interactions between Ir atoms and Mn atoms, the adsorption effect between the two under joule heating promotes the formation of IrMn alloys. However, the dynamic diffusion speeds of Ir and Mn atoms in a carbon matrix are different, and the IrMn atoms have larger atomic radiuses, so that a large number of dislocation defects and lattice distortions exist in the formed IrMn alloy nano particles, the electronic structure of the alloy nano particles is effectively optimized, the metal d band center is obviously regulated and controlled, and the adsorption characteristics of the metal d band center on reaction intermediate products are obviously regulated, so that abundant catalytic activities can be provided for HERs and OERs. Meanwhile, the rapid unstable thermal shock enables zinc nitrate to volatilize rapidly, and the strong blasting effect causes abundant macroporous structures on the carbon matrix, which is beneficial to greatly increasing the specific surface area and fully exposing active sites.
Embodiments of the present application provide for the use of a carbon material catalyst derived in situ from a noble metal/transition metal alloy rich in dislocation defects in the electrolysis of water.
SEM, TEM and spherical aberration electron microscope analysis are carried out on the IrMn-N-C alloy catalyst material prepared by the method.
FIG. 1 is an SEM image of an IrMn-N-C alloy catalyst material prepared according to the present application; the COFs derivatives loaded with IrMn alloy nanoparticles can be seen from the figure. The macroporous carbon matrix is produced. The size of the macropores on the carbon matrix is 100-500nm.
FIG. 2 is a spherical aberration electron microscope image of the IrMn-N-C alloy catalyst material prepared in the present application; it can be seen from the figure that the IrMn alloy is uniformly distributed on the carbon matrix. The size of the IrMn alloy nano-particles is 5-30nm.
FIG. 3 is a TEM image of the IrMn-N-C alloy catalyst material prepared herein; it can be seen from the figure that there are plentiful dislocation defects and lattice distortions in IrMn nano-alloy particles.
FIG. 4 is a graph of the electrocatalytic Hydrogen Evolution (HER) performance of the IrMn-N-C alloy catalyst material prepared herein under acidic conditions; from the figure it can be seen that HER under acidic conditions only requires 25mV overpotential to reach 10mA/cm 2 Current density.
FIG. 5 is a graph showing the electrocatalytic Oxygen Evolution (OER) performance of the IrMn-N-C alloy catalyst material prepared herein under acidic conditions: OER under acidic conditions only requires 310mV overpotential to reach 10mA/cm 2 Current density.
FIG. 6 is a graph showing the water electrolysis performance of the IrMn-N-C alloy catalyst material prepared according to the present application under acidic conditions: only 1.47V is needed to realize 10mA/cm in the acid full hydrolysis 2 Current density.
The heteroatom doped macroporous carbon/alloy composite catalyst has the advantages of rich dislocation defects, high-density active sites, large pore diameter adjustability, synergistic effect among multiple active components and the like. Meanwhile, the COFs-derived macroporous carbon matrix for loading the metal alloy prepared by the method provides rich anchoring sites for in-situ loading of the alloy nanoparticles, ensures sufficient exposure of the alloy nanoparticles, and is favorable for improving catalytic dynamics.
The mass fraction of the IrMn alloy is 3-15wt% through inductively coupled plasma emission spectrometer (ICP-OES) test, and the size of the IrMn alloy nano-particles is 5-30nm. The size of the macropores on the carbon matrix is 100-500nm. The specific surface area of the catalyst is up to 1260m by testing N2 adsorption and desorption curves 2 /g。
Based on the above, the preparation innovatively causes lattice distortion through rapid unstable thermal shock and dislocation effect caused by different atomic radius differences, and further changes the interplanar spacing induced strain effect. This variation causes dislocation of the original atomic arrangement, which forms a rich dislocation defect in the alloy nanoparticles, which is a key reason for its excellent HER and OER catalytic activity. While dislocation defect dominated high energy surface structures are more likely to resist surface reconstruction and matrix oxidation during catalysis. This results in a bimetallic IrMn alloy catalyst having excellent catalytic and durability properties.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present application without departing from the spirit or scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims and the equivalents thereof, the present application is intended to cover such modifications and variations.
Claims (9)
1. A method for preparing a carbon material catalyst for in-situ derivatization of noble metal/transition metal alloy rich in dislocation defects is characterized in that,
COFs matrix preparation: preparing a covalent organic framework COFs matrix by utilizing Schiff base reaction;
preparation of COFs precursor anchoring metal ions: fully mixing the obtained COFs matrix with noble metal salt, transition metal salt and zinc nitrate, and drying to obtain a COFs precursor of the anchoring metal ion;
noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on COFs substrates to form nanoparticles: heating the COFs precursor of the anchored metal ion to a preset temperature by Joule heating, preserving heat for a preset time at the preset temperature, and cooling by rapid cooling; repeating the Joule heating process for the preset times;
carbonizing nano particles: and carrying out high-temperature carbonization treatment on the nano particles to obtain the carbon material catalyst of the noble metal/transition metal alloy which is derived in situ and is rich in dislocation defects.
2. The method of claim 1, wherein,
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 ferric salt, nickel salt, cobalt salt and manganese salt.
3. The method of claim 1, wherein noble metal atoms and transition metal atoms diffuse, crystallize and grow in situ on COFs substrates to form nanoparticles; the method comprises the following steps:
heating the material to 1500-2500 deg.c in joule heating for 3-8 s; then preserving heat at the temperature for 10-40s; finally, rapidly cooling to room temperature within 1-6 s; repeating the above operation for 1-4 times; and obtaining the noble metal/transition metal alloy nano particles which are derived from the COFs matrix in situ and are rich in dislocation defects.
4. The method of claim 1, wherein the nanoparticles are carbonized; the method comprises the following steps:
calcining at 900 ℃ for 2-3 hours in a tubular furnace under Ar atmosphere to thoroughly remove the organic impurities of the nano particles, so that the nano particles are fully carbonized and completely uniform; the macroporous carbon material derived from COFs is obtained by in-situ growth of metal atom and transition metal atom alloy nano particles.
5. The preparation method according to claim 1, wherein the preparation of COFs precursor anchoring metal ions is specifically:
mixing the obtained COFs matrix with iridium chloride, manganese chloride and zinc acetate aqueous solution in acetonitrile solution, fully stirring for 2 hours, centrifugally cleaning, and then vacuum drying at 80 ℃ for 12 hours; the obtained COFs precursor for anchoring metal ions.
6. The method of claim 1, wherein the COFs matrix is prepared by:
dissolving terephthalaldehyde, p-phenylenediamine and glacial acetic acid in absolute ethyl alcohol by a solution method, fully and uniformly stirring, and then carrying out centrifugal vacuum drying to obtain the COFs matrix.
7. A carbon material catalyst for in situ derivatizing a noble metal/transition metal alloy rich in dislocation defects, prepared by the preparation method of any one of claims 1 to 6;
the carbon material catalyst is rich in precious metal/transition metal alloy particles with dislocation defects; wherein the mass fraction of the noble metal/transition metal alloy is 3-15wt%, the size of the noble metal/transition metal alloy nano particles is 5-30nm, and the size of macropores on the carbon matrix is 100-500nm; the specific surface area of the macroporous carbon matrix derived from COFs in the carbon material catalyst is up to 1260m 2 /g。
8. The carbon material catalyst of claim 7, wherein the noble metal/transition metal alloy particles are IrMn alloy nanoparticles; the internal lattice of the IrMn alloy is compressed, the interplanar spacing is reduced, and serious lattice distortion is generated; a number of dislocation defects and lattice dislocation rows are formed in the IrMn alloy nanoparticles.
9. Use of a carbon material catalyst prepared according to the preparation method of any one of claims 1 to 6 or a carbon material catalyst according to any one of claims 7 to 8 for electrolysis of water.
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| CN117463373B (en) * | 2023-12-27 | 2024-04-05 | 山东海化集团有限公司 | Porous hollow tubular CoS 2 /NiS 2 Rapid preparation method and application of heterojunction |
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