CN112691691A - Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst - Google Patents
Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000013153 zeolitic imidazolate framework Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 2
- 244000038561 Modiola caroliniana Species 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
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- 238000004321 preservation Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
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- 238000001354 calcination Methods 0.000 abstract 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/40—
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- B01J35/50—
Abstract
A preparation method of a modified ZIFs-derived Co-N-C-MT/EA catalyst belongs to the technical field of catalysts. The invention adopts the traditional solution precipitation method to synthesize the ZIF-67 precursor material, and then the Co-N-C-MT/EA-2 catalyst is formed by calcining and pyrolyzing the precursor material. The invention takes a methanol-ethanol mixture as a solvent, 2-methylimidazole and cobalt nitrate hexahydrate as raw materials, and takes the solvent ratio, the synthesis time, the solution concentration, the raw material ratio, the pyrolysis temperature and the like as exploration values. The preparation method of the Co-N-C-MT/EA-2 electrocatalyst with controllable particle size is provided, and compared with a Co-N-C-MT catalyst and a Co-N-C-EA catalyst, the prepared Co-N-C-MT/EA-2 electrocatalyst is small in particle size and outstanding in oxygen reduction performance. Therefore, the improvement of the ZIF-67 precursor synthesis method has profound significance to the field of catalyst research.
Description
Technical Field
The invention relates to a preparation method of a Co-N-C-MT/EA oxygen reduction reaction catalyst with controllable particle size, belonging to the technical field of catalysts.
Background
In order to better challenge the ground to the energy crisis, all countries are working on developing clean and efficient new energy technology. The metal-air battery has the characteristics of high energy density, low cost, environmental friendliness and the like, and becomes an energy storage device with great development prospect. The noble metal platinum catalyst is the most efficient catalyst at present in the aspects of electrochemical activity and stability, however, the platinum catalyst is high in cost and scarce in resources, and most of platinum resources are concentrated in a few countries, so that the large-scale production and application of the platinum catalyst are seriously hindered. The ZIF-67 precursor material is a branch of a metal organic framework MOFs material, is formed by coordination of cobalt ions and 2-methylimidazole, and is an SOD type topological structure. The ZIF-67 has the characteristics of controllable pore size and distribution, larger specific surface area, good catalytic performance, high stability and the like, so that the ZIF-67 becomes a novel template of various catalytic and gas separation materials. Many researches in recent years show that a porous carbon material formed by high-temperature carbonization of a ZIF-67 material can keep the original shape, and can be doped with various heteroatoms and metal ions to form a novel porous carbon material to further improve the electrocatalytic performance of the novel porous carbon material, and a plurality of ZIF-67-derived porous carbon materials are developed as high-efficiency electrocatalysts at present.
Currently, most of reported ZIF-67 precursors are nano-stereostructures synthesized in a methanol solvent. For example, the Journal of Materials Chemistry A,2(30),11606-11613 reported that bulk ZIF-67 was synthesized by solvothermal method using ethanol as solvent, 1.7 μm ZIF-67 was synthesized by solution precipitation method at 60 ℃ using water as solvent, 800nm ZIF-67 material was synthesized by solution precipitation method at 60 ℃ using methanol as solvent, and 300nm ZIF-67 dodecahedron rhombohedral material was synthesized by solution precipitation method at room temperature using methanol as solvent. For example, the literature Scientific reports 7.1(2017):1-9 report ZIF-67 precursor materials with a nanoparticle size of 400 nm. For example, the documents Molecular Catalysis,463,77-86 report that a ZIF-67 material having a particle size of 1.7 μm was synthesized by a solution precipitation method using water as a solvent at 60 ℃, a ZIF-67 material having a particle size of 800nm was synthesized again in a methanol solvent under the same conditions, and finally a ZIF-67 material having a particle size of 400nm was synthesized using methanol as a solvent at room temperature. For example, the Nanoscale, 10(21), 10073-10078, discloses a method for synthesizing a cubic ZIF-67 material by using CTAB as a template and using an aqueous solvent at room temperature for 25min through a solution precipitation method. The method comprises the following steps: the Journal of Materials Chemistry A,2(30),11606, 11613, it is mentioned that the nanostructure and average particle size, synthesis conditions, carbonization temperature, crystal size and porosity of ZIF-67 can be controlled by controlling experimental conditions, the resulting ZIF-67 has adjustable pore size, and a highly stable structure can obtain novel catalytic performance.
The preparation of ZIF-67 of different particle sizes is a necessary measure to broaden the range of catalytic applications. At present, no report related to a preparation method for controlling the particle size of ZIF-67 is found. Therefore, the ZIF-67 nano-particles with the shape between a cubic body and a sphere are prepared by controlling the concentration values of a reactant cobalt salt solution and a 2-methylimidazole solution within a certain range, and have wide application value in the field of catalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a Co-N-C-MT/EA electrocatalyst with controllable particle size. Compared with the prior art, the method has the advantages of simple operation, low reaction temperature, low cost and simple synthesis process, can be used as an oxygen reduction catalyst, and has important significance for large-scale production of in-situ electrodes. The object for the preferred embodiment is to further reduce the particle size and to further enhance the catalytic activity and stability of the catalyst.
The technical scheme adopted by the invention is as follows:
(1) preparing a precursor solution: dissolving cobalt nitrate hexahydrate of a certain mass in a solvent to obtain a mauve clear solution A, wherein the mass concentration of Co is 0.081-0.162mol L-1(ii) a Dissolving a certain mass of 2-methylimidazole in the same corresponding solvent to obtain a clear solution B, wherein the mass concentration of the 2-methylimidazole is 0.1913-0.3826mol L-1Stirring uniformly, preferably for 10-20min, and stirring at 30-40 rpm; the solvent is a mixture of methanol and ethanol, and the volume ratio of the methanol to the ethanol is 1: 1;
(2) slowly adding the solution B into the solution A, uniformly stirring, standing and aging, and preferably standing for 12 hours;
(3) centrifuging and washing the precipitate after static aging for several times (the centrifugal rotation speed is 12000r/min, and the liquid used for washing is a mixed solution of ethanol and methanol), and then drying in vacuum, preferably drying in a vacuum drying oven at 80 ℃ for 12h to obtain a ZIF-67 precursor;
(4) and (3) placing the ZIF-67 precursor in an alumina crucible, carbonizing at high temperature in a tubular furnace in Ar atmosphere (Ar gas flow), and gradually cooling to room temperature after keeping the temperature for a period of time to obtain the ZIF-67-derived porous carbon material named as Co-N-C-MT/EA.
Preferably, in the step (1), the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 1:2-2:1, and further preferably the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 1:1, namely, the cobalt nitrate hexahydrate is named as ZIF-67-MT/EA.
Preferably, in the step (1), the solvent is a methanol solvent, an ethanol solvent or a mixed solvent of methanol and ethanol; further preferably, the mixed solvent is a mixed solvent of methanol and ethanol, and the volume ratio is 1:1.
In the step (1), the solution B is slowly added into the solution A, and the mixture gradually changes into different purple red solutions; or the solution A is slowly dripped into the solution B, and the mixture gradually changes into different blue precipitates;
preferably, in the step (2), the stirring speed ranges from 60 rpm to 80rpm, and the stirring time is 60 min.
Preferably, in the step (3), the centrifugal separation time is 3min, the centrifugation is repeated three times, and the washing is performed 3 times by using a methanol and ethanol mixed solvent.
Preferably, in step (4), the reaction is carried out at 5 ℃ min in an Ar atmosphere-1The temperature rise rate is 600-900 ℃, the heat preservation time is 2-4h, and the carbonization temperature is more preferably 700 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the ZIF-67 precursor material is prepared by mixing cobalt nitrate hexahydrate and 2-methylimidazole in a mixed solvent of methanol and ethanol according to a certain proportion, and the cost is low.
The method takes cobalt nitrate hexahydrate, 2-methylimidazole, methanol and ethanol as raw materials, and the synthesis method is efficient and simple.
The existing ZIF-67 is mostly prepared in a methanol solvent, compared with ZIF-67 prepared in the methanol solvent, the ZIF-67 prepared in the methanol and ethanol mixed solvent has obviously reduced particle size, meanwhile, a series of ZIF-67 precursor materials with different particle sizes can be obtained by adjusting the solvent proportion, and the Co-N-C-MT/EA catalyst obtained under the optimized condition further has excellent activity and stability, and has excellent application prospect in the field of oxygen reduction catalysts.
Drawings
FIG. 1 is an SEM photograph of a catalyst ZIF-67-MT/EA-1 prepared by using a mixed system of methanol and ethanol in example 1.
FIG. 2 is an SEM image of the catalyst Co-N-C-MT/EA-1 prepared by using a methanol and ethanol mixed system in example 1.
FIG. 3 is an SEM photograph of the catalyst ZIF-67-MT/EA-2 prepared in example 2 using a mixed system of methanol and ethanol.
FIG. 4 is an SEM image of the catalyst Co-N-C-MT/EA-2 prepared by using a methanol and ethanol mixed system in example 2.
FIG. 5 is an SEM photograph of the catalyst ZIF-67-MT/EA-3 prepared in example 3 using a mixed system of methanol and ethanol.
FIG. 6 is an SEM image of the catalyst Co-N-C-MT/EA-3 prepared by the mixed system of methanol and ethanol in example 3.
FIG. 7 is an SEM photograph of the catalyst ZIF-67-MT prepared in comparative example 1 using the methanol system.
FIG. 8 is an SEM image of the catalyst ZIF-67-EA prepared by using the ethanolic system in comparative example 2.
FIG. 9 LSV-600rpm curves at O for rotating disk electrodes for Co-N-C-MT (methanol), Co-N-C-EA (ethanol), Co-N-C-MT/EA-2 (methanol + ethanol) catalysts prepared for example 2 and comparative examples 1, 2 for three different solvents2Comparative plot of saturated 0.1M KOH.
FIG. 10 is a comparison of LSV-600rpm curves for rotating disk electrodes of Co-N-C-MT/EA-1(1:2), Co-N-C-MT/EA-2(1:1), Co-N-C-MT/EA-3(2:1) catalysts prepared for three different ratios in examples 1, 2, 3 saturated with 0.1M KOH at O2.
FIG. 11 comparative example 3 is a comparison of LSV of a 20 wt% Pt/C catalyst before and after ADT 5000 cycles CV test.
FIG. 12 is a comparative LSV plot of Co-N-C-MT/EA-2 catalyst before and after ADT 5000 cycles CV test.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
Mixing methanol and ethanol (volume ratio of 1:1) as solvent, and adding cobalt nitrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2)(Co(NO3)2·6H2The mass ratio of O to 2-MIM is 1 to 2, and the mass concentration of Co is 0.081mol L-1The mass concentration of the 2-MIM substance was 0.3825mol L-1，Co(NO3)2·6H2The molar ratio of O to 2 to MIM is 1:7), dropwise adding a cobalt salt solvent into a 2-methylimidazole solution, mixing, vigorously stirring for 60min by using a magnetic stirrer, standing and aging for 12h, centrifuging the obtained blue precipitate solution, washing the blue precipitate solution by using a mixed solvent of ethanol and methanol, and drying for 12h in vacuum, wherein the obtained product is named ZIF-67-MT/EA-1. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image in FIG. 1 shows that the obtained material is a three-dimensional structure, and the size of the nanometer particle diameter is 260-280 nm.
Placing the obtained blue ZIF-67-MT/EA-1 material in a tubular furnace, firstly introducing Ar gas to remove air in the tubular furnace, then heating to 700 ℃ at the heating rate of 5 ℃/min, preserving the heat for 120min, and then cooling to room temperature to obtain an obtained sample named as Co-N-C-700-MT/EA-1. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image in FIG. 2 shows that the obtained material is a three-dimensional structure, and the size of the nano-particle size range is 210-230 nm.
2.25mg of Co-N-C-MT/EA-1 catalyst is weighed, ultrasonically dispersed in 500 mu L of Nafion and 1000 mu L of ethanol mixed solution, a proper amount of slurry is dropwise added to the surface of the polished electrode by using a microsyringe, electrochemical tests are carried out in a three-electrode system, and the tests are carried out in an alkaline medium, as shown in figure 9.
Example 2
Mixing methanol and ethanol (volume ratio of 1:1) as solvent, and adding cobalt nitrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2)(Co(NO3)2·6H2The mass ratio of O to 2-MIM is 1 to 1, and the mass concentration of Co is 0.081mol L-1The mass concentration of the 2-MIM substance was 0.1913mol L-1，Co(NO3)2·6H2The molar ratio of O to 2 to MIM is 1:3.5), dropwise adding a cobalt salt solvent into a 2-methylimidazole solution, mixing, vigorously stirring for 60min by using a magnetic stirrer, standing and aging for 12h, centrifuging the obtained light blue precipitate solution, washing the obtained solution by using an ethanol and methanol mixed solvent, and drying for 12h in vacuum, wherein the obtained product is named as ZIF-67-MT/EA-2. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image in FIG. 3 shows that the obtained material is a three-dimensional structure, and the nano-particle size is 240-260 nm.
The obtained light blue ZIF-67-MT/EA-2 material is placed in a tubular furnace, Ar gas is firstly introduced to exhaust air in the tubular furnace, then the temperature is increased to 700 ℃ at the temperature rising rate of 5 ℃/min, the temperature is kept for 120min, and then the temperature is reduced to room temperature, so that the obtained sample named as Co-N-C-MT/EA-2 is also the Co-N-C-MT/EA of the invention. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image in FIG. 4 shows that the obtained material is a three-dimensional structure, and the size of the nanometer particle size is 150-170 nm.
Weighing 2.25mg of Co-N-C-MT/EA-2, namely the Co-N-C-MT/EA catalyst, ultrasonically dispersing the Co-N-C-MT/EA catalyst in a Nafion and ethanol mixed solution, taking a proper amount of slurry by using a microsyringe, dropwise adding the slurry on the surface of the polished electrode, and performing electrochemical tests in a three-electrode system in an alkaline medium, wherein the test is performed as shown in figure 9.
Example 3
Mixing methanol and ethanol (volume ratio of 1:1) as solvent, and adding cobalt nitrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2)(Co(NO3)2·6H2The mass ratio of O:2-MIM is 2:1, and the mass concentration of Co is 0.162mol L-1The mass concentration of the 2-MIM substance was 0.1913mol L-1，Co(NO3)2·6H2The molar ratio of O to 2 to MIM is 1:1.7), dropwise adding a cobalt salt solvent into a 2-methylimidazole solution, mixing, vigorously stirring for 60min by using a magnetic stirrer, standing and aging for 12h, centrifuging the obtained blue precipitate solution, washing the blue precipitate solution by using an ethanol and methanol mixed solvent, and drying for 12h in vacuum to obtain a dark blue product named ZIF-67-MT/EA-3. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image in FIG. 5 shows that the obtained material is a three-dimensional structure, and the nano-particle size is 370-390 nm.
And placing the obtained deep blue ZIF-67-MT/EA-3 material in a tubular furnace, firstly introducing Ar gas to remove air in the tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min, preserving the heat for 120min, and then cooling to room temperature to obtain a sample named as Co-N-C-MT/EA-3. The obtained product is characterized by a morphology structure, and a Scanning Electron Microscope (SEM) image of FIG. 6 shows that the obtained material is a three-dimensional structure, and the size of the nanometer particle size is 270-290 nm.
Weighing 2.25mg of Co-N-C-MT/EA-3 catalyst, ultrasonically dispersing in a mixed solution of Nafion and ethanol, taking a proper amount of slurry by using a microsyringe, dropwise adding the slurry to the surface of the polished electrode, and performing electrochemical tests in a three-electrode system in an alkaline medium, wherein the test is performed as shown in FIG. 9.
Example 4
Weighing 2.25mg of Co-N-C-MT/EA-2 catalyst, ultrasonically dispersing the catalyst in a mixed solution of Nafion and ethanol, taking a proper amount of slurry by using a microsyringe, dropwise adding the slurry on the surface of a polished electrode, and performing electrochemical tests in a three-electrode system, wherein the test is performed in an accelerated aging test (ADT) in a 0.1MKOH alkaline medium, and a 5000-turn CV accelerated test is performed in a voltage range of 0-1.23V at a sweep rate of 200mV/S, as shown in FIG. 12.
Comparative example 1
Taking methanol as solvent, adding cobalt nitrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2)(Co(NO3)2·6H2O:2-MIM mass ratio of 1:1The mass concentration of Co is 0.081mol L-1The mass concentration of the 2-MIM substance was 0.1913mol L-1) Dropwise adding a cobalt salt solvent into a 2-methylimidazole solution for mixing, violently stirring by a magnetic stirrer for 60min, standing and aging for 12h, centrifugally washing the obtained blue precipitate solution, and then drying in vacuum for 12h to obtain the product named ZIF-67-MT. The obtained product is subjected to morphology and structure characterization, and the Scanning Electron Microscope (SEM) image of FIG. 7 shows that the obtained material is a rhombic dodecahedron structure consistent with the literature.
And placing the obtained ZIF-67-MT material in a tubular furnace, introducing Ar gas to remove air in the tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 120min, and cooling to room temperature to obtain a sample named as Co-N-C-MT, wherein the obtained material is a rhombic dodecahedron structure.
Comparative example 2
Using ethanol as solvent, adding cobalt nitrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2)(Co(NO3)2·6H2The mass ratio of O to 2-MIM is 1 to 1, and the mass concentration of Co is 0.081mol L-1The mass concentration of the 2-MIM substance was 0.1913mol L-1) Dropwise adding a cobalt salt solvent into a 2-methylimidazole solution for mixing, violently stirring by a magnetic stirrer for 60min, standing and aging for 12h, centrifugally washing the obtained blue precipitate solution, and then drying in vacuum for 12h to obtain the product named ZIF-67-EA. The obtained product is subjected to morphology and structure characterization, and as can be seen from a Scanning Electron Microscope (SEM) image of fig. 8, the obtained material is a flower-like structure formed by small-particle crystals.
And placing the obtained ZIF-67-EA material in a tubular furnace, introducing Ar gas to remove air in the tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 120min, and cooling to room temperature to obtain a sample named as Co-N-C-EA, wherein the carbonized material is a flower-shaped structure formed by small-particle crystals.
Comparative example 3
2.25mg of 20 wt% Pt/C catalyst was weighed, ultrasonically dispersed in a mixed solution of Nafion and ethanol, an appropriate amount of slurry was dropped onto the polished electrode surface using a microsyringe, electrochemical tests were conducted in a three-electrode system, and accelerated aging tests (ADT) were conducted in a 0.1MKOH alkaline medium, and 5000 cycles of CV accelerated tests were conducted in a voltage range of 0 to 1.23V at a sweep rate of 200mV/S, as shown in FIG. 12.
Claims (10)
1. A preparation method of a modified ZIFs-derived Co-N-C-MT/EA catalyst is characterized by comprising the following steps:
(1) preparing a precursor solution: dissolving cobalt nitrate hexahydrate of a certain mass in a solvent to obtain a mauve clear solution A, wherein the mass concentration of Co is 0.081-0.162mol L-1(ii) a Dissolving a certain mass of 2-methylimidazole in the same corresponding solvent to obtain a clear solution B, wherein the mass concentration of the 2-methylimidazole is 0.1913-0.3826mol L-1Stirring uniformly, preferably for 10-20min, and stirring at 30-40 rpm; the solvent is a mixture of methanol and ethanol, and the volume ratio of the methanol to the ethanol is 1: 1;
(2) slowly adding the solution B into the solution A, uniformly stirring, standing and aging, and preferably standing for 12 hours;
(3) centrifuging and washing the precipitate after static aging for several times, and then drying in vacuum for 12 hours at 80 ℃ preferably in a vacuum drying oven to obtain a ZIF-67 precursor;
(4) and (3) placing the ZIF-67 precursor in an alumina crucible, carbonizing at high temperature in a tube furnace in Ar atmosphere, and gradually cooling to room temperature after keeping the temperature for a period of time to obtain the ZIF-67-derived porous carbon material named as Co-N-C-MT/EA.
2. The preparation method of the modified ZIFs-derived Co-N-C-MT/EA catalyst according to claim 1, wherein in the step (1), the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 1:2-2:1, and more preferably, the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 1:1, namely, the catalyst is named ZIF-67-MT/EA.
3. The method for preparing a modified ZIFs-derived Co-N-C-MT/EA catalyst according to claim 1, wherein in the step (1), the solution B is slowly added to the solution a in the step (1), and the mixture gradually changes into different purple-red solutions; or the solution A is slowly dripped into the solution B, and the mixture gradually changes into different blue precipitates.
4. The preparation method of the modified ZIFs-derived Co-N-C-MT/EA catalyst according to claim 1, wherein in the step (2), the stirring speed ranges from 60 rpm to 80rpm, and the stirring time is 60 min.
5. The method for preparing a modified ZIFs-derived Co-N-C-MT/EA catalyst according to claim 1, wherein in step (3), the centrifugation is repeated three times for 3min, and the washing is performed 3 times with a mixed solvent of methanol and ethanol.
6. The process for preparing a modified ZIFs-derived Co-N-C-MT/EA catalyst according to claim 1, wherein in step (4), at 5 ℃ · min in Ar atmosphere-1The temperature rise rate is 600-900 ℃, and the heat preservation time is 2-4 h.
7. The process of claim 6, wherein the carbonization temperature is selected to be 700 ℃.
8. A modified ZIFs-derived Co-N-C-MT/EA catalyst prepared according to the process of any one of claims 1 to 7.
9. The modified ZIFs-derived Co-N-C-MT/EA catalyst prepared by the method as claimed in any one of claims 1 to 7, wherein the obtained catalyst is a three-dimensional structure with a nano-particle size of 150-170 nm.
10. The modified ZIFs-derived Co-N-C-MT/EA catalyst prepared according to any of claims 1-7, wherein accelerated aging test (ADT) is performed in 0.1MKOH alkaline medium with 5000 cycles CV acceleration at a sweep rate of 200mV/S in the voltage range of 0-1.23V.
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