CN115744876A - Synthetic method and application of two-dimensional layered hollow carbon nanoparticle array superstructure - Google Patents
Synthetic method and application of two-dimensional layered hollow carbon nanoparticle array superstructure Download PDFInfo
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a synthesis method and application of a two-dimensional layered hollow carbon nanoparticle array superstructure, which are characterized in that metal-organic framework (MOF) polyhedral nanoparticles are taken as basic assembly units through an ice template self-assembly strategy, the basic assembly units are firstly assembled into an MOF two-dimensional layered (single-layer and double-layer) ordered superstructure, and then the ordered superstructure is pyrolyzed and finally converted into the two-dimensional layered (single-layer and double-layer) hollow carbon nanoparticle array superstructure. According to the scheme, macroscopic preparation of the MOF two-dimensional layered superstructure can be realized without using any additive or external field acting force; and the preparation of MOF superstructures with different particle sizes and morphologies can be realized, and the universality is very strong. The two-dimensional hollow carbon nanoparticle array superstructure material prepared by the invention has the advantages of high specific surface area, high aspect ratio, high nitrogen content, high conductivity and the like, is beneficial to full exposure of active sites, ion transfer and migration and charge transportation, and shows good electrocatalytic activity in an oxygen reduction reaction.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a synthetic method and application of a two-dimensional layered hollow carbon nano particle array superstructure.
Background
Metal-organic framework (MOF) materials are a new porous crystal material, and have the advantages of regular and controllable pore size, pore channels capable of being modified functionally, ultrahigh specific surface area and the like, so that the MOF materials have great attention in the fields of gas adsorption/separation, heterogeneous catalysis, energy conversion, drug delivery and the like. However, most MOF materials have limited applications under harsh conditions (e.g., electrocatalysis in acid/base electrolytes) due to their low chemical and thermal stability.
Compared with MOF materials, MOF-derived carbon nanomaterials have not only high specific surface area and developed pore structure, but also excellent chemical and thermal stability, as well as good electrical conductivity. In particular, MOF derived hollow structure carbon materials have received great attention due to their unique structural features. Currently, MOF-derived hollow structure carbon materials are mainly synthesized based on several strategies, including: an inward contraction mechanism of the core-shell structure MOF material (MOF is a shell layer), an outward contraction mechanism of the core-shell structure MOF material (MOF is a core layer), a special outward contraction mechanism of the MOF nano array and the like. A detailed synthetic strategy can be found In "HollowCarbon-Based nanoarchitecture Based on ZIF: in-ward/Outward connected mechanics and beyond, small,17 (2021), 2004142. Among them, the synthesis of hollow carbon nanoarrays based on the special outward shrinkage mechanism of MOF nanoarrays still faces huge challenges due to the stringent requirements of the preparation of MOF nanoarrays for the matching of template substrates and MOF crystals.
In recent years, with the application of nano self-assembly technology in MOF polyhedral nanoparticles, MOF superstructures with ordered MOF nanoparticles are successfully prepared. In the document "Self-Assembly of Polyregenerative metals-Organic Framework Particles inter Three-Dimensional-Ordered Supermeasures, nature. Chem.10 (2018), 78", daniel Maspoch et al, applied to the "droplet evaporation induced Self-Assembly strategy", prepared Three-Dimensional Ordered superstructures of MOF colloidal Particles on glass slides; in the literature, "electric field-Induced Assembly of monomer polymeric M-ethyl Organic framework crystals, J.am.chem.Soc.,135 (2013), 34-37", steve Granick et al, applied electric field Induced Assembly strategy ", a one-dimensional chain ZIF-8 superstructure was prepared; in the literature "Self-Assembly of metal-Organic Framework (MOF) Nanoparticle Monolayers and Free-standing multilayers.j.am.chem.soc.,141 (2019), 20000-20003.", seth m.cohen et al use biomolecular anchors (histamine) to grow a thin layer of polymer (polymethylmethacrylate, PMMA) on the MOF surface and produce two-dimensional heterogeneous single and multi-layer superstructures by a "liquid-gas interface Assembly strategy". Although the above strategies can achieve the production of MOF superstructures, these self-assembly techniques rely too much on substrate support, polymer modification, or external forces such as the application of electric/magnetic fields during assembly, and thus cannot achieve a macroscopic production of MOF superstructures. Currently there is a lack of self-assembly synthesis strategies for the macro-preparation of MOF superstructures with some universality.
In order to overcome the defects in the prior art, a preparation method of the MOF superstructure, which is simple to operate, low in cost and environment-friendly, is researched, and the conversion of the MOF superstructure into a two-dimensional layered (single-layer and double-layer) hollow carbon nanoparticle array superstructure at high temperature has important significance.
Disclosure of Invention
The invention aims to solve the defects in the prior art, provides a synthesis method of a two-dimensional layered hollow carbon nanoparticle array superstructure and application thereof in electrocatalysis of an oxygen reduction reaction, and solves the defect of complicated process of the traditional preparation method by a one-step pyrolysis strategy based on a special outward shrinkage mechanism of an MOF nanoparticle array; and the substrate or external acting force is not needed, so that macroscopic quantity preparation can be realized.
The technical scheme disclosed by the invention is as follows: the method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array comprises the following steps:
(1) Preparing MOF nano particles;
(2) Preparation of two-dimensional layered MOF superstructure:
diffusing the MOF nanoparticles prepared in the step (1) in water to form a stable colloidal solution, adopting an ice template self-assembly strategy, quickly freezing the MOF colloidal solution by liquid nitrogen, and then putting the frozen MOF colloidal solution into a freeze dryer for freeze-drying to obtain a two-dimensional layered MOF superstructure;
(3) Preparing a two-dimensional layered hollow carbon nanoparticle array superstructure:
and (3) placing the two-dimensional layered MOF superstructure prepared in the step (2) in a tube furnace, carbonizing at high temperature in an inert gas atmosphere, and naturally cooling to room temperature to obtain the two-dimensional layered hollow carbon nanoparticle array superstructure.
Further, the two-dimensional layered MOF superstructure and the two-dimensional layered hollow carbon nanoparticle array superstructure obtained in steps (2) and (3) may be a single-layer or double-layer structure.
Preferably, the MOF nanoparticles prepared in step (1) are any one of ZIF-8, ZIF-67, uiO-66 and MIL-88.
Preferably, the particle size of the MOF nanoparticles obtained in step (1) is 50-500nm.
Preferably, the morphology of the MOF nanoparticles obtained in step (1) is rhombohedral, cubic or octahedral.
Further, the mass concentration of the MOF nano-particle colloid solution in the step (2) is 1-2%.
Further, the freeze-drying time in the step (2) is 24-48h.
Further, the inert gas in the step (3) is nitrogen or argon, the flow rate of the inert gas is 50-150mL/min, the carbonization temperature is 800-900 ℃, the temperature rise rate is 3-5 ℃/min, and the carbonization time is 2-3h.
The two-dimensional layered hollow carbon nanoparticle array superstructure material prepared by the method can be applied to the aspect of oxygen reduction reaction electrocatalysis, and specifically, the two-dimensional layered hollow carbon nanoparticle array superstructure material is mixed with a binder and ethanol, slurry is obtained by ultrasonic homogenization, and then the mixture is coated on a rotating disc electrode, so that the oxygen reduction reaction working electrode is obtained. Compared with the traditional carbon nano particle material electrode, the half-wave potential of the two-dimensional layered hollow carbon nano particle array superstructure material can be effectively improved.
The beneficial effects of the invention are as follows:
1. compared with the traditional method, the method does not need substrate support or external field acting force (such as an external electric field, an external magnetic field and the like) holding, and can realize the macro preparation of the two-dimensional layered MOF superstructure with the MOF nanoparticles arranged in order;
2. the ice template self-assembly strategy adopted by the application has universality, and the preparation of the two-dimensional layered MOF superstructure can be realized by MOF polyhedral nanoparticles with different crystal structures, different morphologies and different particle sizes;
3. the ice template self-assembly strategy adopted by the application can realize the controllable preparation of single-layer and double-layer MOF superstructures by regulating and controlling the concentration of the MOF colloidal solution;
4. the ice template self-assembly strategy adopted by the application has the characteristics of low price, high efficiency, greenness and environmental protection;
5. according to the method, the hollow-structure carbon nanoparticle array can be prepared without preparing MOF precursors (such as core-shell structures) with complex structures and additional template removal processes and one-step pyrolysis based on a special outward shrinkage mechanism, the overall preparation process is simple, and the preparation efficiency is remarkably improved;
6. the two-dimensional layered hollow carbon nanoparticle array superstructure material prepared by the method has the advantages of high specific surface area, high aspect ratio, high nitrogen content, high conductivity and the like, is beneficial to full exposure of active sites, ion transfer and migration and charge transportation, can be used as a high-efficiency electrocatalyst of an oxygen reduction reaction, and can effectively improve the electrocatalysis performance compared with the traditional carbon nanoparticle material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph (on a 300nm scale) of a single layer cut angle rhombohedral ZIF-8 superstructure prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph (on a 2 μm scale) of a monolayer hollow carbon nanoparticle array superstructure prepared in example 1;
FIG. 3 is a Transmission Electron Microscopy (TEM) photograph (on 300nm scale) of the monolayer hollow carbon nanoparticle array superstructure prepared in example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph (200 nm scale) of the bilayer hollow carbon nanoparticle array superstructure prepared in example 2;
fig. 5 is a linear cyclic voltammogram of the single-layer hollow carbon nanoparticle array superstructure material obtained in example 1 and the carbon nanoparticle material obtained in comparative example 1.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
(1) Preparation of corner cut rhombohedral dodecahedral ZIF-8 nanoparticles
Adding 1.50g of zinc acetate into 25mL of water, adding 5.60g of 2-methylimidazole into 25mL of hexadecyltrimethylammonium bromide (CTAB) aqueous solution with the concentration of 0.49mmol/L, dissolving by ultrasonic waves, mixing the two solutions under stirring, stirring for 1min, and standing at room temperature for 2h. And centrifuging and washing to obtain the rhombic dodecahedron ZIF-8 nano-particles.
(2) Preparation of single-layer cut-corner rhombic dodecahedron ZIF-8 superstructure
Adding 300mg of the truncated rhombohedral ZIF-8 nanoparticles obtained in the step (1) into 30g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution to a freeze drying oven, and performing freeze drying for 24h to obtain the single-layer truncated rhombohedral ZIF-8 superstructure.
(3) Preparation of monolayer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer corner-cut rhombic dodecahedron ZIF-8 superstructure precursor obtained in the step (2) into a tubular furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nanoparticle array superstructure material.
Fig. 1 is a Scanning Electron Microscope (SEM) image of a single-layer corner cut rhombic dodecahedron ZIF-8 superstructure, and fig. 2 is a Scanning Electron Microscope (SEM) image of a single-layer hollow carbon nanoparticle array superstructure, from which it can be seen that the particle size of corner cut rhombic dodecahedron ZIF-8 nanoparticles is 182 ± 10nm. FIG. 3 is a Transmission Electron Microscopy (TEM) image of a single layer hollow carbon nanoparticle array superstructure transformed from a single layer cut-angle rhombohedral ZIF-8 superstructure by one-step pyrolysis, from which it can be seen that the ordered arrangement of carbon nanoparticles has a hollow structure.
Example 2
(1) Preparation of corner cut rhombohedral dodecahedral ZIF-8 nanoparticles
1.50g of zinc acetate was added to 25mL of water, 5.60g of 2-methylimidazole was added to 25mL of a 0.49mmol/L cetyltrimethylammonium bromide (CTAB) aqueous solution and dissolved by sonication, the two solutions were mixed with stirring, and after stirring for 1min, the mixture was allowed to stand at room temperature for 2 hours. And centrifuging and washing to obtain the rhombic dodecahedral ZIF-8 nanoparticles with the particle size of 182 +/-10 nm.
(2) Preparation of double-layer cut-angle rhombic dodecahedron ZIF-8 superstructure
Adding 300mg of the truncated rhombohedral ZIF-8 nanoparticles obtained in the step (1) into 15g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 2%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution to a freeze drying oven, and performing freeze drying for 24h to obtain the double-layer truncated rhombohedral ZIF-8 superstructure.
(3) Preparation of double-layer hollow carbon nanoparticle array superstructure material
And (3) placing the double-layer cut-angle rhombic dodecahedron ZIF-8 superstructure precursor obtained in the step (2) into a tube furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the double-layer hollow carbon nanoparticle array superstructure material.
Fig. 4 is a Scanning Electron Microscope (SEM) image of a two-layer hollow carbon nanoparticle array superstructure.
Example 3
(1) Preparation of cubic ZIF-8 nanoparticles
0.725g of zinc nitrate was added to 25mL of water, 6.478g of 2-methylimidazole and 0.02g of cetyltrimethylammonium bromide (CTAB) were added to 100mL of water and dissolved by sonication, and the two solutions were mixed with stirring and left to stand at room temperature for 12 hours after stirring for 25 minutes. And centrifuging and washing to obtain cubic ZIF-8 nanoparticles with the particle size of 150 +/-12 nm.
(2) Preparation of monolayer cubic ZIF-8 superstructure
Adding 300mg of the cubic ZIF-8 nano-particles obtained in the step (1) into 30g of water, performing ultrasonic treatment for 10min at room temperature to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution into a freeze drying box, and performing freeze drying for 24h to obtain a single-layer cubic ZIF-8 superstructure.
(3) Preparation of monolayer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer cubic ZIF-8 superstructure precursor obtained in the step (2) into a tube furnace, calcining at the constant temperature of 900 ℃ for 3h in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nanoparticle array superstructure material.
Example 4
(1) Preparation of rhombic regular dodecahedral ZIF-8 nanoparticles
Adding 1.50g of zinc acetate into 25mL of water, adding 5.60g of 2-methylimidazole into 25mL of water, dissolving by ultrasonic wave, mixing the two solutions under stirring, stirring for 1min, and standing for 4h at room temperature. And centrifuging and washing to obtain the rhombic regular dodecahedral ZIF-8 nano-particles, wherein the particle size of the nano-particles is 280 +/-15 nm.
(2) Preparation of single-layer rhombic regular dodecahedron ZIF-8 superstructure
Adding 300mg of the rhombic regular dodecahedron ZIF-8 nano-particles obtained in the step (1) into 30g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution to a freeze drying oven, and performing freeze drying for 24h to obtain the single-layer rhombic regular dodecahedron ZIF-8 superstructure.
(3) Preparation of single-layer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer rhombic regular dodecahedron ZIF-8 superstructure precursor obtained in the step (2) into a tubular furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nanoparticle array superstructure material.
Example 5
(1) Preparation of rhombic regular dodecahedral ZIF-67 nanoparticles
Adding 1.50g of zinc acetate into 25mL of water, adding 5.60g of 2-methylimidazole into 25mL of aqueous solution, dissolving by ultrasonic waves, mixing the two solutions under stirring, stirring for 1min, and standing for 2h at room temperature. And centrifuging and washing to obtain rhombic regular dodecahedral ZIF-67 nano particles, wherein the particle size of the nano particles is 250 +/-12 nm.
(2) Preparation of single-layer rhombic regular dodecahedron ZIF-67 superstructure
Adding 300mg of the rhombic regular dodecahedron ZIF-67 nano particles obtained in the step (1) into 30g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution to a freeze drying oven, and performing freeze drying for 24h to obtain a single-layer rhombic regular dodecahedron ZIF-67 superstructure.
(3) Preparation of single-layer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer rhombic regular dodecahedron ZIF-67 superstructure precursor obtained in the step (2) into a tubular furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the cobalt nanoparticle modified single-layer hollow carbon nanoparticle array superstructure material.
Example 6
(1) Preparation of octahedral UiO-66 nanoparticles
To 100mL of a DMF solution having an acetic acid concentration of 2.1mol/L, 0.34g of zirconium chloride was added and dissolved by sonication, and 0.25g of terephthalic acid was added and dissolved by sonication, and the mixture was allowed to stand at 120 ℃ for 12 hours. And centrifuging and washing to obtain octahedral UiO-66 nano particles, wherein the particle size of the nano particles is 300 +/-15 nm.
(2) Preparation of single-layer octahedron UiO-66 superstructure
And (2) adding 300mg of the octahedral UiO-66 nanoparticles obtained in the step (1) into 30g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and performing freeze drying for 24h to obtain the single-layer octahedral UiO-66 superstructure.
(3) Preparation of monolayer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer octahedral UiO-66 superstructure precursor obtained in the step (2) into a tubular furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the zirconia nanoparticle modified single-layer hollow carbon nanoparticle array superstructure material.
Example 7
(1) Preparation of spindle-shaped MIL-88 nanoparticles
0.64g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) F127 was added to 60mL of water, 0.72g of ferric chloride was added and stirred for 1h, 2.4mL of acetic acid solution was added and stirred for 1h, 0.24g of 2-aminoterephthalic acid was added and stirred for 2h, and the mixture was transferred to an autoclave and allowed to stand at 110 ℃ for 24h. And centrifuging and washing to obtain spindle-shaped MIL-88 nano particles, wherein the particle size of the nano particles is 300 +/-12 nm.
(2) Preparation of monolayer fusiform MIL-88 superstructure
Adding 300mg of the fusiform MIL-88 nano-particles obtained in the step (1) into 30g of water, performing ultrasonic treatment at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, then quickly freezing the colloidal solution by using liquid nitrogen, transferring the frozen colloidal solution to a freeze drying box, and performing freeze drying for 24h to obtain the single-layer fusiform MIL-88 superstructure.
(3) Preparation of single-layer hollow carbon nanoparticle array superstructure material
And (3) placing the single-layer spindle-shaped MIL-88 superstructure precursor obtained in the step (2) into a tubular furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the iron nanoparticle modified single-layer hollow carbon nanoparticle array superstructure material.
Comparative example 1
(1) Preparation of corner cut rhombohedral dodecahedral ZIF-8 nanoparticles
1.50g of zinc acetate was added to 25mL of water, 5.60g of 2-methylimidazole was added to 25mL of a 0.49mmol/L cetyltrimethylammonium bromide (CTAB) aqueous solution and dissolved by sonication, the two solutions were mixed with stirring, and after stirring for 1min, the mixture was allowed to stand at room temperature for 2 hours. And centrifuging and washing to obtain the rhombic dodecahedral ZIF-8 nanoparticles with the particle size of 182 +/-11 nm.
(2) Preparation of hollow carbon nanoparticle material
And (2) placing the rhombic dodecahedron ZIF-8 precursor obtained in the step (1) in a tube furnace, calcining at the constant temperature of 900 ℃ for 3 hours in a nitrogen atmosphere at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain the hollow carbon nano-particle material.
Application example 1
Preparing an oxygen reduction reaction electrode:
5mg of the single-layer hollow carbon nanoparticle array superstructure material obtained in example 1, 40 mu L of a binder (Nafion reagent) and 960 mu L of an ethanol solution are mixed, and ultrasonic treatment is performed to obtain uniform slurry, and then the uniform slurry is coated on a rotating disc electrode to obtain an oxygen reduction reaction working electrode.
5mg of the hollow carbon nanoparticle material prepared in comparative example 1, 40. Mu.L of a binder (Nafion reagent) and 960. Mu.L of an ethanol solution were mixed, and subjected to ultrasonic treatment to obtain a uniform slurry, which was then applied to a rotating disk electrode to obtain an oxygen reduction reaction working electrode.
And (3) testing the performance of the oxygen reduction reaction:
a three-electrode system is adopted, the oxygen reduction reaction working electrode is used as a working electrode, a platinum wire is used as a counter electrode, ag/AgCl is used as a reference electrode, and the electrolyte is 0.1mol/L KOH solution. The oxygen reduction catalytic performance was tested under an oxygen atmosphere.
Fig. 5 is a linear cyclic voltammogram of the single-layer hollow carbon nanoparticle array superstructure obtained in example 1 and the carbon nanoparticle array superstructure obtained in comparative example 1 at a sweep rate of 2mv/s, and it can be seen from the graph that the half-wave potential of the single-layer hollow carbon nanoparticle array superstructure is 0.76V (vs. rhe), which is increased by 0.04V compared with the carbon nanoparticle material, and has good oxygen reduction electrocatalytic activity.
The foregoing shows and describes the general principles, principal features and advantages of the invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array is characterized by comprising the following steps of:
(1) Preparing MOF nano particles;
(2) Preparation of two-dimensional layered MOF superstructure:
diffusing the MOF nanoparticles prepared in the step (1) in water to form a stable colloidal solution, adopting an ice template self-assembly strategy, quickly freezing the MOF colloidal solution by liquid nitrogen, and then putting the frozen MOF colloidal solution into a freeze dryer for freeze-drying to obtain a two-dimensional layered MOF superstructure;
(3) Preparing a two-dimensional layered hollow carbon nanoparticle array superstructure:
and (3) placing the two-dimensional layered MOF superstructure prepared in the step (2) in a tube furnace, carbonizing at high temperature in an inert gas atmosphere, and naturally cooling to room temperature to obtain the two-dimensional layered hollow carbon nanoparticle array superstructure.
2. The method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the two-dimensional layered MOF superstructure and the two-dimensional layered hollow carbon nanoparticle array superstructure obtained in steps (2) and (3) are of a single-layer or double-layer structure.
3. The method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array of claim 1, wherein the MOF nanoparticles obtained in step (1) are any one of ZIF-8, ZIF-67, uiO-66 and MIL-88.
4. The method for synthesizing a superstructure of a two-dimensional layered hollow carbon nanoparticle array according to claim 1, wherein the particle size of the MOF nanoparticles obtained in step (1) is 50-500nm.
5. The method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array of claim 1, wherein the morphology of the MOF nanoparticles obtained in the step (1) is rhombic regular dodecahedron, cube or octahedron.
6. The method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array of claim 1, wherein the mass concentration of the MOF nanoparticle colloid solution in the step (2) is 1-2%.
7. The method for synthesizing the superstructure of the two-dimensional layered hollow carbon nanoparticle array of claim 1, wherein the freeze-drying time in the step (2) is 24-48h.
8. The method for synthesizing a superstructure of a two-dimensional layered hollow carbon nanoparticle array according to claim 1, wherein the inert gas in the step (3) is nitrogen or argon, the flow rate of the inert gas is 50-150mL/min, the carbonization temperature is 800-900 ℃, the temperature rise rate is 3-5 ℃/min, and the carbonization time is 2-3h.
9. A two-dimensional layered hollow carbon nanoparticle array superstructure material, characterized in that it is prepared by the method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to any one of claims 1 to 8.
10. The application of the two-dimensional layered hollow carbon nanoparticle array superstructure material in electrocatalysis of oxygen reduction reaction, as claimed in claim 9, wherein the two-dimensional layered hollow carbon nanoparticle array superstructure material is mixed with binder and ethanol, ultrasonically homogenized to obtain slurry, and then the slurry is coated on a rotating disk electrode to obtain the oxygen reduction reaction working electrode.
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