CN115744876B - Synthesis method and application of two-dimensional layered hollow carbon nanoparticle array superstructure - Google Patents
Synthesis method and application of two-dimensional layered hollow carbon nanoparticle array superstructure Download PDFInfo
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 34
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- 229920000557 Nafion® Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
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- 229960001340 histamine Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- 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 nano particle array super structure, which uses metal-organic framework (MOF) polyhedral nano particles as basic assembly units through an ice template self-assembly strategy, and the metal-organic framework (MOF) polyhedral nano particles are assembled into the MOF two-dimensional layered (single-layer and double-layer) ordered super structure, and then the MOF two-dimensional layered (single-layer and double-layer) ordered super structure is finally converted into the two-dimensional layered (single-layer and double-layer) hollow carbon nano particle array super structure through pyrolysis. According to the scheme, macro preparation of the MOF two-dimensional layered super structure can be realized without using any additive or external field acting force; and can realize the preparation of MOF superstructures with different particle sizes and different morphologies, and has strong universality. The two-dimensional hollow carbon nano particle array super-structure 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 favorable for full exposure of active sites, ion transfer and migration, charge transportation, and shows good electrocatalytic activity in oxygen reduction reaction.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a synthesis method and application of a two-dimensional layered hollow carbon nano particle array superstructure.
Background
As an emerging porous crystalline material, a Metal-organic framework (Metal-OrganicFramework, MOF) material has been attracting attention in the fields of gas adsorption/separation, heterogeneous catalysis, energy conversion, drug delivery, and the like, because of advantages such as regular and controllable pore size, functionally modifiable pore channels, ultra-high specific surface area, and the like. However, most MOF materials are limited in their application under severe conditions (e.g., electrocatalytic in acid/alkaline electrolytes) due to their relatively low chemical and thermal stability.
Compared with MOF materials, the MOF-derived carbon nanomaterial not only has high specific surface area and developed pore structure, but also has excellent chemical and thermal stability and good 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 synthesized mainly based on several strategies, including in particular: an inward shrinkage mechanism of a MOF material with a core-shell structure (MOF is a shell layer), an outward shrinkage mechanism of a MOF material with a core-shell structure (MOF is a core layer), a special outward shrinkage mechanism of a MOF nano array and the like. The detailed synthetic strategy can be referred to In the literature "Hollow Carbon-Based Nanoarchitectures Based on ZIF: in-ward/Outward Contraction Mechanism and Beyond. Small,17 (2021), 2004142". Among them, the synthesis of hollow carbon nanoarrays based on a special outward contraction mechanism of MOF nanoarrays still faces a great challenge 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 nano-particles, MOF super-structures with ordered MOF nano-particles are successfully prepared. In the literature "Self-Assembly of Polyhedral Metal-Organic Framework Particles into Three-Dimensional Ordered superstructural. Nat. Chem.,10 (2018), 78.", daniel Maspoch et al used a "droplet evaporation induced Self-assembly strategy", a three-dimensional ordered superstructure of MOF micelles was prepared on glass slides; in the literature "Electric Field-Induced Assembly of Monodisperse Polyhedral M-etal Organic Framework crystals.j.am.chem.soc.,135 (2013), 34-37," Steve grandick et al prepared a one-dimensional chain ZIF-8 superstructure using an "applied Electric Field induced assembly strategy"; in the literature "Self-Assembly of Metal-Organic Framework (MOF) Nanoparticle Monolayers and Free-holding multilayers.j.am. Chem. Soc.,141 (2019), 20000-20003," Seth m. Cohen et al grow a thin layer of polymer (polymethyl methacrylate, PMMA) on the surface of the MOF using a biomolecular anchor (histamine), and two-dimensional heterogeneous single-layer and multi-layer superstructures were prepared by a "liquid-gas interface assembly strategy". Although the above strategies can achieve the preparation of the MOF superstructure, these self-assembly techniques are too dependent on substrate support, polymer modification, or external forces such as electric/magnetic fields applied during assembly, and thus cannot achieve the macro preparation of the MOF superstructure. Currently, a self-assembly synthesis strategy for preparing MOF superstructures in a macro-scale with certain universality is lacking.
In order to overcome the defects in the prior art, a preparation method of an MOF super structure which is simple to operate, low in cost and environment-friendly is explored, and the MOF super structure is converted into a two-dimensional layered (single-layer and double-layer) hollow carbon nano particle array super structure at high temperature, so that the method has important significance.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a synthesis method of a two-dimensional layered hollow carbon nano particle array superstructure and application of the method in the aspect of oxygen reduction reaction electrocatalysis, and the defect of complicated process of the traditional preparation method is solved by a one-step pyrolysis strategy based on a special outward contraction mechanism of an MOF nano particle array; and the macro preparation can be realized without the help of a substrate or an external acting force.
The technical scheme disclosed by the invention is as follows: the synthesis method of the two-dimensional layered hollow carbon nano particle array superstructure comprises the following steps:
(1) Preparing MOF nano particles;
(2) Preparation of a two-dimensional layered MOF superstructure:
diffusing the MOF nano particles prepared in the step (1) into water to form a stable colloid solution, adopting an ice template self-assembly strategy, rapidly freezing the MOF colloid solution through liquid nitrogen, and then putting the MOF colloid solution into a freeze dryer for freeze drying to obtain a two-dimensional layered MOF superstructure;
(3) Preparing a two-dimensional layered hollow carbon nano particle array superstructure:
and (3) placing the two-dimensional layered MOF superstructure prepared in the step (2) in a tubular furnace, carbonizing at high temperature in an inert gas atmosphere, and naturally cooling to room temperature to obtain the two-dimensional layered hollow carbon nano particle array superstructure.
Further, the two-dimensional layered MOF superstructure and the two-dimensional layered hollow carbon nanoparticle array superstructure obtained in the steps (2) and (3) may be a single-layer or a double-layer structure.
Preferably, the MOF nanoparticle prepared in step (1) is any one of ZIF-8, ZIF-67, uiO-66 and MIL-88.
Preferably, the MOF nanoparticles obtained in step (1) have a particle size of 50-500nm.
Preferably, the morphology of the MOF nanoparticle obtained in step (1) is rhombohedral dodecahedron, cube or octahedron.
Further, the mass concentration of the MOF nanoparticle colloid solution in the step (2) is 1% -2%.
Further, the freeze drying time in the step (2) is 24-48h.
Further, in the step (3), the inert gas is nitrogen or argon, the flow rate of the inert gas is 50-150mL/min, the carbonization temperature is 800-900 ℃, the heating rate is 3-5 ℃/min, and the carbonization time is 2-3h.
The two-dimensional layered hollow carbon nano particle array super structure material prepared by the method can be applied to the aspect of oxygen reduction reaction electrocatalysis, specifically, the two-dimensional layered hollow carbon nano particle array super structure material is mixed with a binder and ethanol, and the slurry is obtained by ultrasonic homogenization and then smeared on a rotating disk 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 super-structure material can be effectively improved.
The beneficial effects of the invention are as follows:
1. compared with the traditional method, the preparation of the MOF super structure is completed by adopting an ice template self-assembly strategy, and 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) to be supported, so that macro preparation of the two-dimensional layered MOF super structure with MOF nano particles orderly arranged can be realized;
2. the ice template self-assembly strategy adopted by the method has universality, and MOF polyhedral nano particles with different crystal structures, different morphologies and different particle diameters can be used for preparing the two-dimensional layered MOF super structure;
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 MOF colloidal solution;
4. the ice template self-assembly strategy adopted by the application has the characteristics of low cost, high efficiency and environmental protection;
5. according to the preparation method, a MOF precursor (such as a core-shell structure) with a complex configuration is not required to be prepared, an additional template removing process is not required, the hollow structure carbon nano particle array can be prepared and obtained based on one-step pyrolysis of a special outward contraction mechanism, the whole preparation process is simple, and the preparation efficiency is remarkably improved;
6. the two-dimensional layered hollow carbon nanoparticle array super-structure 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 favorable for full exposure of active sites, ion transfer and migration, and charge transportation, can be used as a high-efficiency electrocatalyst for oxygen reduction reaction, and can effectively improve the electrocatalyst performance compared with the traditional carbon nanoparticle material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph (under 300nm scale) of a single-layer corner cut diamond dodecahedron ZIF-8 superstructure prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph (on a 2 μm scale) of the superstructure of the single-layer hollow carbon nanoparticle array prepared in example 1;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph (on a 300nm scale) of the superstructure of the single-layer hollow carbon nanoparticle array prepared in example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph (under 200nm scale) of the superstructure of the double-layered hollow carbon nanoparticle array 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 invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
Example 1
(1) Preparation of corner cut rhombic dodecahedron ZIF-8 nano particles
To 25mL of water was added 1.50g of zinc acetate, and to 25mL of cetyltrimethylammonium bromide (CTAB) aqueous solution having a concentration of 0.49mmol/L was added 5.60g of 2-methylimidazole for ultrasonic dissolution, and the two solutions were mixed with stirring, stirred for 1min, and then allowed to stand at room temperature for 2h. And obtaining the corner-cut rhombic dodecahedron ZIF-8 nano particles through centrifugation and washing.
(2) Preparation of single-layer corner-cut rhombic dodecahedron ZIF-8 super structure
Adding 300mg of the corner-cut rhombic 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%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and freeze-drying for 24h to obtain the single-layer corner-cut rhombic dodecahedron ZIF-8 super structure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the single-layer corner-cut rhombic dodecahedron ZIF-8 super-structure precursor obtained in the step (2) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nano-particle array super-structure material.
Fig. 1 is a Scanning Electron Microscope (SEM) image of a single-layer corner-cut rhombic dodecahedron ZIF-8 super structure, and fig. 2 is a Scanning Electron Microscope (SEM) image of a single-layer hollow carbon nanoparticle array super structure, and it can be seen from the two images that the particle size of the corner-cut rhombic dodecahedron ZIF-8 nanoparticles is 182±10nm. Fig. 3 is a Transmission Electron Microscope (TEM) diagram of a single-layer hollow carbon nanoparticle array superstructure obtained by converting a single-layer chamfer rhombic dodecahedron ZIF-8 superstructure through one-step pyrolysis, and it can be seen from the diagram that the orderly arranged carbon nanoparticles have a hollow structure.
Example 2
(1) Preparation of corner cut rhombic dodecahedron ZIF-8 nano particles
To 25mL of water was added 1.50g of zinc acetate, and to 25mL of cetyltrimethylammonium bromide (CTAB) aqueous solution having a concentration of 0.49mmol/L was added 5.60g of 2-methylimidazole for ultrasonic dissolution, and the two solutions were mixed with stirring, stirred for 1min, and then allowed to stand at room temperature for 2h. And obtaining the corner-cut rhombic dodecahedron ZIF-8 nano particles through centrifugation and washing, wherein the particle size of the nano particles is 182+/-10 nm.
(2) Preparation of double-layer corner-cut rhombic dodecahedron ZIF-8 super structure
Adding 300mg of the corner-cut rhombic dodecahedron ZIF-8 nano particles obtained in the step (1) into 15g of water, performing ultrasonic treatment at room temperature for 10min to form a colloid solution with the mass concentration of 2%, rapidly freezing the colloid solution by using liquid nitrogen, transferring the colloid solution to a freeze drying box, and freeze-drying for 24h to obtain the double-layer corner-cut rhombic dodecahedron ZIF-8 superstructure.
(3) Preparation of double-layer hollow carbon nano particle array super-structure material
And (3) placing the double-layer corner-cut rhombic dodecahedron ZIF-8 super-structure precursor obtained in the step (2) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the double-layer hollow carbon nano-particle array super-structure material.
Fig. 4 is a Scanning Electron Microscope (SEM) image of a superstructure of a double-layered hollow carbon nanoparticle array.
Example 3
(1) Preparation of cubic ZIF-8 nanoparticles
To 25mL of water, 0.725g of zinc nitrate was added, to 100mL of water, 6.178 g of 2-methylimidazole and 0.02g of cetyltrimethylammonium bromide (CTAB) were added and dissolved by ultrasonic waves, the two solutions were mixed with stirring, and after stirring for 25 minutes, the mixture was allowed to stand at room temperature for 12 hours. And (3) centrifuging and washing to obtain cubic ZIF-8 nano particles, wherein the particle size of the nano particles is 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 at room temperature for 10min to form a colloidal solution with the mass concentration of 1%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution into a freeze drying box, and performing freeze drying for 24h to obtain the single-layer cubic ZIF-8 super structure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the single-layer cubic ZIF-8 super-structure precursor obtained in the step (2) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nano-particle array super-structure material.
Example 4
(1) Preparation of rhombic regular dodecahedron ZIF-8 nano particles
1.50g of zinc acetate was added to 25mL of water, and another 25mL of water was added to 5.60g of 2-methylimidazole to be ultrasonically dissolved, and the two solutions were mixed with stirring, and after stirring for 1min, they were allowed to stand at room temperature for 4 hours. And obtaining the rhombic regular dodecahedron ZIF-8 nano particles through centrifugation and washing, wherein the particle size of the nano particles is 280+/-15 nm.
(2) Preparation of single-layer diamond-shaped regular dodecahedron ZIF-8 super structure
Adding 300mg of the diamond-shaped 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%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and freeze-drying for 24h to obtain the single-layer diamond-shaped regular dodecahedron ZIF-8 super structure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the single-layer diamond-shaped regular dodecahedron ZIF-8 super-structure precursor obtained in the step (2) into a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the single-layer hollow carbon nano-particle array super-structure material.
Example 5
(1) Preparation of diamond-shaped regular dodecahedron ZIF-67 nano particles
1.50g of zinc acetate was added to 25mL of water, 5.60g of 2-methylimidazole was added to 25mL of the aqueous solution and dissolved by ultrasonic, the two solutions were mixed with stirring, and after stirring for 1min, the mixture was allowed to stand at room temperature for 2h. And obtaining diamond-shaped regular dodecahedron ZIF-67 nano particles through centrifugation and washing, wherein the particle size of the nano particles is 250+/-12 nm.
(2) Preparation of single-layer diamond-shaped regular dodecahedron ZIF-67 superstructure
Adding 300mg of the diamond-shaped 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%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and freeze-drying for 24h to obtain the single-layer diamond-shaped regular dodecahedron ZIF-67 superstructure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the single-layer diamond-shaped regular dodecahedron ZIF-67 super-structure precursor obtained in the step (2) into a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the cobalt nanoparticle modified single-layer hollow carbon nanoparticle array super-structure 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 ultrasonic, 0.25g of terephthalic acid was added and dissolved by ultrasonic, and the mixture was allowed to stand at 120℃for 12 hours. Obtaining octahedral UiO-66 nanometer particles through centrifugation and washing, wherein the particle size of the nanometer particles is 300+/-15 nm.
(2) Preparation of monolayer octahedral UiO-66 superstructures
Adding 300mg of the octahedral UiO-66 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%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and freeze-drying for 24h to obtain the single-layer octahedral UiO-66 super structure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the monolayer octahedral UiO-66 super-structure precursor obtained in the step (2) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the zirconia nanoparticle modified monolayer hollow carbon nanoparticle array super-structure material.
Example 7
(1) Preparation of spindle-shaped MIL-88 nanoparticles
To 60mL of water was added 0.64g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) F127, 0.72g of ferric chloride was added and stirred for 1 hour, 2.4mL of acetic acid solution was added and stirred for 1 hour, 0.24g of 2-amino terephthalic acid was added and stirred for 2 hours, and the mixture was transferred to an autoclave and allowed to stand at 110℃for 24 hours. 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 single-layer spindle MIL-88 super structure
Adding 300mg of spindle-shaped 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%, rapidly freezing the colloidal solution by using liquid nitrogen, transferring the colloidal solution to a freeze drying box, and freeze-drying for 24h to obtain the single-layer spindle-shaped MIL-88 super structure.
(3) Preparation of single-layer hollow carbon nano particle array super-structure material
And (3) placing the single-layer spindle-shaped MIL-88 super-structure precursor obtained in the step (2) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, heating at a rate of 3 ℃/min, and naturally cooling to room temperature to obtain the iron nanoparticle modified single-layer hollow carbon nanoparticle array super-structure material.
Comparative example 1
(1) Preparation of corner cut rhombic dodecahedron ZIF-8 nano particles
To 25mL of water was added 1.50g of zinc acetate, and to 25mL of cetyltrimethylammonium bromide (CTAB) aqueous solution having a concentration of 0.49mmol/L was added 5.60g of 2-methylimidazole for ultrasonic dissolution, and the two solutions were mixed with stirring, stirred for 1min, and then allowed to stand at room temperature for 2h. And obtaining the corner-cut rhombic dodecahedron ZIF-8 nano particles through centrifugation and washing, wherein the particle size of the nano particles is 182+/-11 nm.
(2) Preparation of hollow carbon nanoparticle materials
And (3) placing the corner-cut rhombic dodecahedron ZIF-8 precursor obtained in the step (1) in a tube furnace, calcining for 3 hours at a constant temperature of 900 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the hollow carbon nano particle material.
Application example 1
Preparation of an oxygen reduction reaction electrode:
5mg of the single-layer hollow carbon nanoparticle array super-structure material obtained in example 1, 40 mu L of a binder (Nafion reagent) and 960 mu L of ethanol solution are mixed, ultrasonic treatment is carried out to obtain uniform slurry, and then the uniform slurry is smeared on a rotating disk 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 an ultrasonic treatment was performed to obtain a uniform slurry, which was then applied to a rotating disk electrode to obtain an oxygen reduction reaction working electrode.
Oxygen reduction reaction Performance test:
the 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. Its 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 material obtained in example 1 and the carbon nanoparticle material 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 material is 0.76V (vs. rhe), which is 0.04V higher than that of the carbon nanoparticle material, and has good oxygen reduction electrocatalytic activity.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. However, the foregoing is merely specific examples of the present invention, and the technical features of the present invention are not limited thereto, and any other embodiments that are derived by those skilled in the art without departing from the technical solution of the present invention are included in the scope of the present invention.
Claims (10)
1. The synthesis method of the two-dimensional layered hollow carbon nano particle array superstructure is characterized by comprising the following steps of:
(1) Preparing MOF nano particles;
(2) Preparation of a two-dimensional layered MOF superstructure:
diffusing the MOF nano particles prepared in the step (1) into water to form a stable colloid solution, adopting an ice template self-assembly strategy, rapidly freezing the MOF colloid solution through liquid nitrogen, and then putting the MOF colloid solution into a freeze dryer for freeze drying to obtain a two-dimensional layered MOF superstructure;
(3) Preparing a two-dimensional layered hollow carbon nano particle array superstructure:
and (3) placing the two-dimensional layered MOF superstructure prepared in the step (2) in a tubular furnace, carbonizing at high temperature in an inert gas atmosphere, and naturally cooling to room temperature to obtain the two-dimensional layered hollow carbon nano particle 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 a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the MOF nanoparticles obtained in the step (1) are any one of ZIF-8, ZIF-67, uiO-66 and MILs-88.
4. The method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the MOF nanoparticles obtained in step (1) have a particle size of 50 to 500 and nm.
5. The method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the MOF nanoparticle obtained in the step (1) has a rhombic regular dodecahedron, a cube or an octahedron shape.
6. The method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the mass concentration of the MOF nanoparticle colloidal solution in the step (2) is 1% -2%.
7. The method for synthesizing a two-dimensional layered hollow carbon nanoparticle array superstructure according to claim 1, wherein the lyophilization time in step (2) is 24-48h.
8. The method for synthesizing the super structure of the two-dimensional layered hollow carbon nano particle array according to claim 1, wherein in the step (3), the inert gas is nitrogen or argon, the flow rate of the inert gas is 50-150mL/min, the carbonization temperature is 800-900 ℃, the heating rate is 3-5 ℃/min, and the carbonization time is 2-3h.
9. A two-dimensional layered hollow carbon nanoparticle array superstructure, characterized in that it is prepared by the synthesis method of 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 nano particle array superstructure in the aspect of oxygen reduction reaction electrocatalysis according to claim 9, wherein the two-dimensional layered hollow carbon nano particle array superstructure material is mixed with a binder and ethanol, and the slurry is obtained by ultrasonic homogenization and then smeared on a rotating disk electrode, so as to obtain the oxygen reduction reaction working electrode.
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