CN114784297B - Preparation method of monoatomic cobalt ORR catalyst - Google Patents
Preparation method of monoatomic cobalt ORR catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 62
- 239000010941 cobalt Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 25
- 108010010803 Gelatin Proteins 0.000 claims abstract description 16
- 239000008273 gelatin Substances 0.000 claims abstract description 16
- 229920000159 gelatin Polymers 0.000 claims abstract description 16
- 235000019322 gelatine Nutrition 0.000 claims abstract description 16
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- 239000011701 zinc Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013384 organic framework Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004931 aggregating effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241001442234 Cosa Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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 relates to a preparation method of a single-atom cobalt ORR catalyst, and belongs to the technical field of electrocatalysis. The method takes gelatin as a carbon source, co (NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 The bimetallic organic framework material generated by the reaction of O and 2-methylimidazole is a cobalt source, the existence of zinc element effectively inhibits cobalt element from aggregating into cobalt nano particles in the pyrolysis process, and finally, the monoatomic catalyst with a Co-N-C structure is constructed, the monoatomization of the cobalt element enables cobalt atoms to be utilized maximally, the density and the intrinsic activity of the active site of the catalyst are effectively improved, and the catalyst shows excellent ORR catalytic performance. The method has simple synthesis steps and low raw material cost, and adopts a double-template strategy to successfully construct the cobalt electrocatalyst with microporous, mesoporous and macroporous multilevel pore structures in an atomic level dispersed manner, so that the pore channel structure is effectively optimized, the specific surface area is increased, and the mass transfer performance is improved.
Description
Technical Field
The invention relates to a preparation method of a single-atom cobalt ORR catalyst, and belongs to the technical field of electrocatalysis.
Background
Oxygen reduction (ORR) is a critical cathode reaction for fuel cells and metal-air cells, but it has the problem of slow kinetics, and efficient catalytic materials are still needed to facilitate the reaction. Therefore, the design of an excellent ORR electrocatalyst is critical to the performance of various next-generation energy storage and conversion devices, including metal-air batteries and fuel cells. Platinum-based noble metal catalysts are commercial ORR electrocatalysts with the best performance at present, but the defects of high cost, scarce reserves, poor durability and the like seriously prevent the wide application of the platinum-based noble metal catalysts in practical energy systems. Therefore, it is of great importance to develop low cost, high performance, non-noble metal-based ORR electrocatalytic materials, such as transition metal oxides, phosphides, sulfides and carbides.
Transition metal-nitrogen-carbon catalysts (M-N-C) are considered to be the most promising alternatives to platinum-based catalysts. The atomic-level M-N-C catalyst, namely the transition metal active species, is reduced to a single atomic scale and anchored in a carbon carrier in a chemical bond form, and has the characteristics of high atomic utilization rate, adjustable electronic structure and the like, so that the catalyst has excellent catalytic performance in catalytic reaction and is widely focused. Metal Organic Frameworks (MOFs) have become precursors for preparing atomic-scale ORR catalysts containing M-N-C structures as an organic-inorganic hybrid material with high nitrogen content and large specific surface area. However, most MOFs derived catalysts reported so far have single pore structure, easy agglomeration of active sites, poor mass transfer, low intrinsic performance of the active sites, low density of active sites, and the like (Xie, xiaoying, et al, "MIL-101-Derived Mesoporous Carbon Supporting Highly Exposed Fe Single-Atom Sites as Efficient Oxygen Reduction Reaction catalysts." Advanced Materials 33.23.23 (2021): 2101038.). Therefore, the construction of the multi-stage structure of the catalyst material and the composition and distribution of the active sites is important for improving the mass transfer and catalytic reaction process of the oxygen reduction reaction of the catalyst and finally improving the catalytic performance of the oxygen reduction reaction.
The single-atom catalyst has high atom utilization rate, high active site density and excellent catalytic performance, and is an important member of catalyst families, while the single-atom cobalt catalyst has proved to have excellent oxygen reduction catalytic performance and is widely studied in the catalysis of oxygen reduction reactions. In the following, the synthesis method of the single-atom cobalt catalyst comprises an impregnation method, a coprecipitation method, a doping method and the like, however, the synthesis of the single-atom cobalt catalyst by the traditional method has the problems of easy aggregation of metals, low specific surface area, poor mass transfer effect and the like, thereby influencing the oxygen reduction catalytic performance of the single-atom cobalt catalyst.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a single-atom cobalt ORR catalyst.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A method for preparing a monoatomic cobalt ORR catalyst, comprising the following steps:
(1) Spherical SiO 2 The nano particles and hexadecyl trimethyl ammonium bromide are dissolved in water and stirred for 1 to 2 hours at normal temperature to obtain a mixed solution A.
Preferably, the spherical SiO 2 The particle size of the nanoparticle was 500nm.
Preferably, the spherical SiO 2 The mass ratio of the nano particles to the hexadecyl trimethyl ammonium bromide is 1:1.
(2) Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water to obtain a mixed solution B, the mixed solution B is added into the mixed solution A obtained in the step (1), and stirring is continued for 1-2 h at normal temperature to obtain a mixed solution C.
Wherein Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 6:1-10:1.
(3) Dissolving 2-methylimidazole in water, adding the obtained solution into the mixed solution C obtained in the step (2), and continuously stirring for 3-4 hours at normal temperature. After the reaction is finished, the solid powder is obtained through centrifugal cleaning and drying.
(4) Adding the solid powder obtained in the step (3) and gelatin into water, stirring for 3-4 hours at 50-60 ℃ in water bath to obtain a gel-like mixture, and freeze-drying the obtained mixture for 12-16 hours.
Wherein the ratio of the mass (g) of the solid powder to the volume (mL) of the water is 0.1-0.17;
the ratio of the mass (g) of the gelatin to the volume (mL) of the water is 0.05-0.085;
preferably, the gelatin is microbial grade gelatin.
(5) And (3) placing the product obtained after the freeze drying in the step (4) in a tubular furnace, pyrolyzing at a high temperature in a nitrogen atmosphere, soaking the pyrolyzed product in an HF aqueous solution with the mass fraction of 20% for 20-24 h, washing and drying to obtain the monoatomic cobalt ORR catalyst (CoSA).
The temperature rise program of the high-temperature pyrolysis is as follows:
raising the temperature from room temperature to 200-300 ℃ at a temperature raising rate of (2-5) DEG C/min, and preserving the heat for 1-2 h at 200-300 ℃;
continuously heating to 700-1000 ℃ at the temperature rising rate of (2-5) DEG C/min, and preserving heat for 2-3 h at 700-1000 ℃.
Advantageous effects
1. The invention provides a preparation method of a single-atom cobalt ORR catalyst, which takes gelatin as a carbon source, co (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 The bimetallic organic framework material generated by the reaction of O and 2-methylimidazole is a cobalt source, in the pyrolysis process, the existence of zinc effectively inhibits cobalt element from being aggregated into cobalt nanoparticles, co atoms and N atoms are connected in a covalent bond mode, and finally, a single-atom catalyst with a Co-N-C structure is constructed, and cobalt atoms are utilized to the maximum extent by single-atomization of the cobalt elements, so that the density and intrinsic activity of active sites of the catalyst are effectively improved, and the catalyst shows excellent ORR catalytic performance.
2. The invention provides a preparation method of a single-atom cobalt ORR catalyst, which adopts a silicon template method in step (1), adopts an ice template method in step (4), constructs a multi-stage pore structure atomically dispersed cobalt electrocatalyst with micropores, mesopores and macropores through a double-template strategy, effectively optimizes the pore channel structure of a pure MOFs material, improves the mass transfer performance, remarkably improves the specific surface area of the single-atom cobalt catalyst, and has the specific surface area up to 851.2m 2 /g, which increases ORR catalytic activity; the method has simple synthesis steps and low raw material cost.
Drawings
FIG. 1 is a scanning electron microscope image of the monoatomic cobalt ORR catalyst prepared in example 1.
FIG. 2 is a transmission electron microscope image of the monoatomic cobalt ORR catalyst prepared in example 1.
FIG. 3 is a transmission electron microscope image of the monoatomic cobalt ORR catalyst prepared in example 2.
FIG. 4 is a transmission electron microscope image of the monoatomic cobalt ORR catalyst prepared in example 3.
FIG. 5 is a spherical aberration correcting transmission electron microscope image of the monoatomic cobalt ORR catalyst prepared in example 1.
FIG. 6 is an X-ray powder diffraction pattern of the monoatomic cobalt ORR catalysts prepared in examples 1 to 3.
FIG. 7 is a nitrogen isothermal adsorption/desorption curve of the single atom cobalt ORR catalyst prepared in example 1.
FIG. 8 is a pore size distribution curve of the monoatomic cobalt ORR catalyst prepared in example 1.
FIG. 9 shows the ORR performance test results of the monoatomic cobalt ORR catalysts prepared in examples 1 to 3 in 0.1mol/L KOH.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples, but is not intended to limit the scope of the patent.
Gelatin, available from Shanghai Ala Biotechnology Co., ltd., model G108395, for microbiology, gel strength 250G Bloom.
Commercial Pt/C material is a platinum/carbon catalyst manufactured by Beijing Yinuoki technology Co., ltd, the model is model A07498, and the mass fraction of platinum in the catalyst is 20%.
The monoatomic cobalt ORR catalysts prepared in the following examples were subjected to the following performance tests:
(1) Morphology testing: scanning electron microscope, model: JEOL model S-4800scanning electron microscope.
Transmission electron microscope, model: HITACHI H-7700transmission electron microscope.
Spherical aberration correction transmission electron microscope, model: themis Z single spherical ACTEM.
(2) Structural test: x-ray powder diffractometer, model: rigaku MiniFlex 600Powder X-ray Diffractometer.
Specific surface area and pore size distribution: specific surface and pore analyzer, model; BELSORP-max II.
(3) ORR performance measurement:
instrument model: rotary ring and disc testing system: U.S. pin rotating ring disk Apparatus (AFCPRBE).
Electrochemical workstation: shanghai Chenhua 760E.
The testing method comprises the following steps:
and on a rotary ring disk test system, testing the ORR catalytic performance of the catalyst by adopting a three-electrode test system, wherein a glassy carbon electrode, a carbon rod and a saturated calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode. Dispersing 2mg of the single-atom cobalt ORR catalyst in 1mL of a solvent to prepare a solution of 2mg/mL, wherein the solvent consists of 0.5mL of water, 0.5mL of isopropyl alcohol and 50 mu L of Nafion solution with the mass fraction of 5%, dripping the obtained mixed solution containing the catalyst on a glassy carbon electrode, and the loading capacity of the catalyst on the glassy carbon electrode is 0.4mg cm -2 Commercial Pt/C catalyst loading was 0.12mg cm -2 . In the test process, the rotating ring disk system is set to 1600rpm, and the linear volt-ampere scanning speed is 5mV s -1 The test was performed in 0.1M KOH solution.
Example 1
A method for preparing a monoatomic cobalt ORR catalyst, comprising the following steps:
(1) Weighing 0.5g spherical SiO with particle size of 500nm 2 The nanoparticles and 0.5g of cetyltrimethylammonium bromide were dissolved in 10mL of water and stirred at room temperature for 1h to obtain a mixed solution A.
(2) 1.9833g of Zn (NO) 3 ) 2 ·6H 2 O and 0.2426g of Co (NO 3 ) 2 ·6H 2 O was dissolved in 5mL of water to give a mixed solution B in which Zn (NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 8:1; and (3) adding the mixed solution B into the mixed solution A obtained in the step (1), and continuously stirring for 1h at normal temperature to obtain a mixed solution C.
(3) 2.46330 g of 2-methylimidazole is weighed and dissolved in 5mL of water, the obtained solution is added into the mixed solution C obtained in the step (2), and stirring is continued for 3h at normal temperature. After the reaction, the mixture was centrifuged at 9000rpm for 5min, washed with ultrapure water and dried at 60℃for 12h to obtain a solid powder.
(4) 0.5g of the solid powder obtained in step (3) and 0.25g of microorganism-grade gelatin were added to 5mL of water, stirred for 3 hours at 50℃in a water bath to obtain a gel-like mixture, and the obtained mixture was freeze-dried for 12 hours.
(5) Placing the product obtained after the freeze drying in the step (4) in a tube furnace, calcining and pyrolyzing at a high temperature in a nitrogen atmosphere, and heating up the product to the following steps:
raising the temperature from room temperature to 300 ℃ at a heating rate of 2 ℃/min, and preserving the heat for 1h; continuously heating to 900 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2h; after high-temperature pyrolysis is finished, the obtained product is soaked in HF aqueous solution with the mass fraction of 20% for 24 hours, washed and dried to obtain the monoatomic cobalt ORR catalyst.
Example 2
A method for preparing a monoatomic cobalt ORR catalyst, comprising the following steps:
(1) Weighing 0.5g spherical SiO with particle size of 500nm 2 The nanoparticles and 0.5g of cetyltrimethylammonium bromide were dissolved in 10mL of water and stirred at room temperature for 1.5h to obtain a mixed solution A.
(2) 1.9124g of Zn (NO) 3 ) 2 ·6H 2 O and 0.3119g of Co (NO 3 ) 2 ·6H 2 O was dissolved in 5mL of water to give a mixed solution B in which Zn (NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 6:1; and (3) adding the mixed solution B into the mixed solution A obtained in the step (1), and continuously stirring for 1.5h at normal temperature to obtain a mixed solution C.
(3) 2.46330 g of 2-methylimidazole is weighed and dissolved in 5mL of water, the obtained solution is added into the mixed solution C obtained in the step (2), and stirring is continued for 3.5h at normal temperature. After the reaction, the mixture was centrifuged at 9000rpm for 5min, washed with ultrapure water and dried at 60℃for 12h to obtain a solid powder.
(4) 0.5g of the solid powder obtained in step (3) and 0.25g of gelatin were added to 4mL of water, and the mixture was stirred for 3.5 hours at 55℃in a water bath to obtain a mixture, and the obtained mixture was freeze-dried for 14 hours.
(5) Placing the product obtained after the freeze drying in the step (4) in a tube furnace, calcining and pyrolyzing at a high temperature in a nitrogen atmosphere, and heating up the product to the following steps:
raising the temperature from room temperature to 250 ℃ at a heating rate of 2 ℃/min, and preserving the heat for 1.5h; continuously heating to 1000 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2.5h; after high-temperature pyrolysis is finished, the obtained product is soaked in HF aqueous solution with the mass fraction of hydrofluoric acid being 20% for 20 hours, and then the monoatomic cobalt ORR catalyst is obtained after washing and drying.
Example 3
A method for preparing a monoatomic cobalt ORR catalyst, comprising the following steps:
(1) Weighing 0.5g spherical SiO with particle size of 500nm 2 The nanoparticles and 0.5g of cetyltrimethylammonium bromide were added to 10mL of water and stirred at room temperature for 2 hours to obtain a mixed solution A.
(2) 2.0283g of Zn (NO) 3 ) 2 ·6H 2 O and 0.1984g of Co (NO 3 ) 2 ·6H 2 O was dissolved in 5mL of water to give a mixed solution B in which Zn (NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 10:1, a step of; and (3) adding the mixed solution B into the mixed solution A obtained in the step (1), and continuously stirring for 2 hours at normal temperature to obtain a mixed solution C.
(3) 2.46330 g of 2-methylimidazole is weighed and dissolved in 5mL of water, the obtained solution is added into the mixed solution C obtained in the step (2), and stirring is continued for 4h at normal temperature. After the reaction, the mixture was centrifuged at 9000rpm for 5min, washed with ultrapure water and dried at 60℃for 12h to obtain a solid powder.
(4) 0.5g of the solid powder obtained in step (3) and 0.25g of gelatin were added to 3mL of water, and the mixture was stirred for 3 hours at 60℃in a water bath to obtain a mixture, and the obtained mixture was freeze-dried for 16 hours.
(5) Placing the product obtained after the freeze drying in the step (4) in a tube furnace, calcining and pyrolyzing at a high temperature in a nitrogen atmosphere, and heating up the product to the following steps:
raising the temperature from room temperature to 200 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2h; continuously heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours; after high-temperature pyrolysis is finished, the obtained product is soaked in HF aqueous solution with the mass fraction of 20% for 22 hours, washed and dried to obtain the monoatomic cobalt ORR catalyst.
Scanning Electron Microscope (SEM) tests were performed on the single-atom cobalt ORR catalysts prepared in examples 1 to 3, and SEM test results of the single-atom cobalt ORR catalyst prepared in example 1 are shown in fig. 1, confirming that the catalyst has a cellular three-dimensional porous structure. SEM test results of the monoatomic cobalt ORR catalysts prepared in example 2 and example 3 were similar to example 1.
The single-atom cobalt ORR catalysts prepared in examples 1-3 were subjected to Transmission Electron Microscopy (TEM) testing, and as shown in fig. 2-4, the morphology of porous carbon was seen in fig. 2-4, with silicon spheres etched to leave round holes of about 500nm in diameter in the carbon matrix, while no cobalt nanoparticles were observed by TEM, indicating that cobalt was not present in the form of nanoparticles, but rather in the form of single atoms in the catalysts.
The monoatomic cobalt ORR catalysts prepared in examples 1 to 3 were subjected to a spherical Aberration Correction Transmission Electron Microscope (ACTEM) test, the results of the ACTEM test of the monoatomic cobalt ORR catalyst prepared in example 1 are shown in fig. 5, and it can be seen that a large number of white bright spots, namely atomic cobalt sites, can be observed in the graph, and the TEM and ACTEM tests prove that the monoatomic cobalt electrocatalyst is successfully synthesized. The ACTEM characterization results of example 2 and example 3 are similar to those of example 1.
The monoatomic cobalt ORR catalysts prepared in examples 1 to 3 were subjected to X-ray powder diffraction test (XRD), and the results are shown in fig. 6, which show that there are only diffraction peaks of graphitized carbon, no diffraction peaks of metallic cobalt, and the presence of atomically dispersed cobalt in the catalyst was again confirmed in agreement with the results of the above morphological characterization.
The single-atom cobalt ORR catalyst prepared in example 1 is subjected to a nitrogen isothermal adsorption and desorption experiment, the adsorption and desorption curve is shown in figure 7, and the material has a huge specific surface area and reaches 851.2m 2 /g; the obtained pore size distribution diagram is shown in figure 8, and the test result shows that the mesoporous, mesoporous and macroporous structures exist in the catalyst, and the multi-layer pore size structure improves the mass transfer process in ORR catalysis and improves the ORR catalytic activity. The characterization results of example 2 and example 3 are similar to those of example 1, the specific surface areas are respectivelyUp to 635.2m 2 /g and 602.3m 2 And/g, mesoporous and macroporous structures are all present in the catalyst.
ORR performance tests were performed on the monoatomic cobalt ORR catalysts and commercial Pt/C materials prepared in examples 1-3, which exhibited good ORR catalytic performance with example 1 performing optimally, as shown in fig. 9, with half-wave potentials of 0.87V, 0.85V, 0.84V, and 0.85V achieved for examples 1-3 and commercial Pt/C materials, respectively, under alkaline conditions.
Claims (5)
1. A preparation method of a monoatomic cobalt ORR catalyst is characterized by comprising the following steps of: the method comprises the following steps:
(1) Spherical SiO 2 Dissolving the nano particles and hexadecyl trimethyl ammonium bromide in water, and stirring for 1-2 h at normal temperature to obtain a mixed solution A;
(2) Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O is dissolved in water to obtain a mixed solution B, the mixed solution B is added into the mixed solution A in the step (1), and stirring is continued for 1-2 h at normal temperature to obtain a mixed solution C;
wherein Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mol ratio of O is 6:1-10:1;
(3) Dissolving 2-methylimidazole in water, adding the obtained solution into the mixed solution C, and continuously stirring for 3-4 hours at normal temperature; centrifugally cleaning and drying to obtain solid powder;
(4) Adding solid powder and gelatin into water, stirring for 3-4 hours at 50-60 ℃ in water bath to obtain a gel-like mixture, and freeze-drying the obtained mixture for 12-16 hours;
wherein the ratio of the mass (g) of the solid powder to the volume (mL) of the water is 0.1-0.17;
the ratio of the mass (g) of the gelatin to the volume (mL) of the water is 0.05-0.085;
(5) Placing the freeze-dried product into a tubular furnace, pyrolyzing at high temperature in a nitrogen atmosphere, soaking the pyrolyzed product in HF water solution with the mass fraction of 20% for 20-24 h, washing and drying to obtain a monoatomic cobalt ORR catalyst;
the temperature rise program of the high-temperature pyrolysis is as follows:
raising the temperature from room temperature to 200-300 ℃ at a temperature raising rate of (2-5) DEG C/min, and preserving the heat for 1-2 h at 200-300 ℃;
continuously heating to 700-1000 ℃ at the temperature rising rate of (2-5) DEG C/min, and preserving heat for 2-3 h at 700-1000 ℃.
2. The method for preparing the monoatomic cobalt ORR catalyst according to claim 1, wherein the method comprises the following steps: the spherical SiO 2 The particle size of the nanoparticle was 500nm.
3. A process for the preparation of a monoatomic cobalt ORR catalyst according to claim 1 or 2, characterised in that: the spherical SiO 2 The mass ratio of the nano particles to the hexadecyl trimethyl ammonium bromide is 1:1.
4. A process for the preparation of a monoatomic cobalt ORR catalyst according to claim 1 or 2, characterised in that: the gelatin is microbial gelatin.
5. The method for preparing the monoatomic cobalt ORR catalyst according to claim 1, wherein the method comprises the following steps: the spherical SiO 2 The particle size of the nano particles is 500nm; the spherical SiO 2 The mass ratio of the nano particles to the hexadecyl trimethyl ammonium bromide is 1:1; the gelatin is microbial gelatin.
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