CN112038648B - Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof - Google Patents
Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst with a hollow structure, and a preparation method and application thereof. The method provided by the invention can effectively improve the utilization rate of the active sites of the transition metal cobalt and nitrogen co-doped carbon catalyst, the prepared catalyst can efficiently catalyze the oxygen reduction reaction of the cathode of the fuel cell, and the oxygen reduction catalytic activity is superior to that of commercial Pt/C.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst, and a preparation method and application thereof.
Background
The fuel cell is a power generation device, and the product is environmentally-friendly and pollution-free water, and does not discharge gases such as carbon dioxide and sulfur dioxide, so that the fuel cell is widely concerned by researchers. However, the fuel cell electrode reaction requires noble metal platinum as a catalyst, which has high cost and scarce resources, and seriously restricts the large-scale commercialization of the fuel cell. Therefore, the development of a non-noble metal oxygen reduction catalyst with high catalytic activity and low price is of great significance.
Among many non-noble metal oxygen reduction catalysts, Transition Metal (TM), typically Fe or Co, nitrogen Co-doped carbon material (TM-N-C) has attracted much attention because of its superior oxygen reduction catalytic activity. The catalyst is generally prepared by high-temperature treatment of a mixture of a transition metal source, nitrogen and a carbon precursor. For example, Chinese patent application CN201910836903 uses polystyrene microspheres with different particle sizes as templates and discloses a preparation method and application of a cobalt and nitrogen doped three-dimensional ordered porous carbon catalyst. The prepared catalyst is a three-dimensional carbon material with a regular structure and clear particles, and has the advantages of ordered pore channels, high specific surface area, high activity, high stability and the like. The method provides great possibility for synthesizing the oxygen reduction electrocatalytic material with controllable pores, high specific surface area and good durability. The raw materials are easy to obtain and low in price, and the method has an industrial application prospect.
In recent years, metal organic framework Materials (MOFs) have the characteristics of high specific surface area, adjustable pore structure, diversified structural compositions and the like, and become an ideal precursor for preparing TM-N-C. For example, chinese patent application CN202010087294 prepares a core-shell nanostructure material with cobalt compound coated with porous carbon material, and specifically discloses a Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and a preparation method thereof, which comprises the following formula raw materials: fe-based MOFs, hydroxyethylidene diphosphonic acid, chitosan, glycine, an esterification catalyst, a composite base catalyst and a condensing agent. According to the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and the preparation method thereof, N/P Co-doping enables a carbon material to form rich pore channels and a large number of mesoporous structures, so that the formation of active sites and the medium transmission of oxygen reduction reaction are facilitated, a core-shell nano structure with a cobalt compound coated by a porous carbon material has a richer morphology structure, so that the catalyst has better mass transfer performance, the cobalt compound formed after the Co-based MOFs with the nano structure are calcined is uniformly loaded into the pore channels of the porous carbon material, the graphitization degree of the carbon material is improved by the cobalt compound, the conductivity of the carbon material is increased, and the forward progress of the oxygen reduction reaction is promoted.
However, the pyrolysis process of the MOFs has the problem that the structure is easy to collapse, so that the active sites cannot be fully exposed, and the catalytic activity exertion is influenced. Therefore, the catalyst still needs to further improve the utilization rate of active sites, strengthen mass transfer and further improve the catalytic activity of oxygen reduction.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and a preparation method and application thereof. The structure can greatly improve the specific surface area of the catalyst, thereby promoting the improvement of the utilization rate of the active sites. The transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst prepared by the invention can efficiently catalyze oxygen reduction reaction, and shows oxygen reduction catalytic activity and electrochemical stability superior to commercial Pt/C. The preparation method is simple and controllable, and has the advantages of abundant raw material reserves and low cost.
The invention adopts the following technical scheme: a transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst with a hollow structure is prepared by taking sulfonated polystyrene microspheres as templates and carrying out self-assembly on the surfaces of the polystyrene microspheres by using a metal cobalt source and a nitrogen-containing organic ligand.
In the reaction system, a sulfonated group is introduced on the surface of a polystyrene microsphere, the transition metal cobalt and nitrogen co-doped carbon catalyst takes the sulfonated polystyrene microsphere as a template, and the zeolite imidazole ester metal organic framework material is grown on the surface of the template by utilizing the electrostatic action between the sulfonic group on the surface of the microsphere and metal cobalt ions.
In a preferred embodiment of the invention, the transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst is prepared by pyrolysis and carbonization in an inert atmosphere.
In a preferred embodiment of the invention, the nitrogen-containing organic ligand is one or more of 2-methylimidazole, benzimidazole, imidazole and 2-imidazolinethione; the metal cobalt source is soluble salt of cobalt; more preferably, the metal cobalt source is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate.
The application also protects a preparation method of the hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst, in a reaction system, sulfonated polystyrene microspheres are used as templates, and a metal cobalt source and a nitrogen-containing organic ligand are self-assembled on the surfaces of the polystyrene microspheres to form a precursor, and the precursor is prepared by pyrolysis and carbonization in an inert atmosphere.
In a preferred embodiment of the invention, the preparation method comprises the steps of fully dispersing the template sulfonated polystyrene microspheres in an organic solvent, then adding a soluble salt solution of transition metal cobalt, slowly pouring an organic solution containing a nitrogen ligand into the sulfonated polystyrene microsphere emulsion while stirring, and reacting to obtain the microspheres with the zeolite imidazole ester framework compound material growing on the surface of the template.
In a preferred embodiment of the present invention, the preparation method comprises the following steps:
(1) preparing polystyrene microspheres: washing a styrene monomer and a divinyl benzene monomer, and then washing the styrene to be neutral by using deionized water; uniformly stirring water and a cross-linking agent, adding styrene, heating and reacting for 1-2h under an inert atmosphere, and adding a deionized water solution dissolved with potassium persulfate to continue the reaction; adding a saturated NaCl solution into the reaction product, and carrying out suction filtration and drying on the precipitate to obtain polystyrene microspheres;
(2) preparing sulfonated polystyrene microsphere emulsion: mixing and stirring template polystyrene microspheres and concentrated sulfuric acid, centrifugally separating a product after reaction, washing the product with ethanol, and drying the product to prepare sulfonated polystyrene microspheres, dissolving the sulfonated polystyrene microspheres in an organic solvent, and uniformly dispersing the sulfonated polystyrene microspheres to obtain sulfonated polystyrene microsphere emulsion;
(3) preparing a precursor: respectively dissolving soluble salt of cobalt and an organic ligand in an organic solvent, and preparing polystyrene microspheres with the surface growth of the zeolite imidazolate metal organic framework material under the stirring condition;
(4) and (3) pyrolysis carbonization process: subjecting the precursor prepared in the step (3) to inert atmosphere at 1-10 deg.C for min -1 The temperature is raised to 600-900 ℃ and the temperature is kept for 1-3 h to obtain the transition metal cobalt and nitrogen co-doped carbon catalyst.
In a preferred embodiment of the invention, in the step (1), the washing is to wash the styrene monomer and the divinylbenzene monomer by using a sodium hydroxide solution with a mass fraction of 10%, and then wash the styrene to be neutral by using deionized water; the morphology of the final product is a microspherical shape with uniform size and good dispersion, and the diameter is about 500 nm.
In a preferred embodiment of the present invention, in the step (2), the organic solvent is one or more of methanol, ethanol and propylene glycol; the sulfonation temperature is 30-50 ℃, the reaction time is 8-10 h, the sulfonation solution is 98% concentrated sulfuric acid solution, and the mass ratio of the polystyrene microspheres to the concentrated sulfuric acid is 0.01-0.02.
In a preferred embodiment of the invention, in the step (3), firstly, the cobalt solution is poured into the polystyrene microsphere emulsion in the step (2), and then the solution containing the organic ligand is slowly poured into the polystyrene microsphere emulsion; the molar ratio of the soluble salt of cobalt to the organic ligand is 0.05-0.25, and the reaction time is 2-22 h; the mass ratio of the cobalt salt to the polystyrene microsphere is 1.5-2.5.
In a preferred embodiment of the present invention, in the step (4), the inert atmosphere is argon or nitrogen, and the holding time is 2-3 h.
The invention also protects the cobalt and nitrogen co-doped carbon oxygen reduction catalyst for the cathode oxygen reduction reaction of the alkaline fuel cell.
Compared with the prior art, the invention has the following advantages:
(1) the preparation process is simple and controllable, and the raw materials are abundant in reserves and low in cost.
(2) The method adopts concentrated sulfuric acid to sulfonate the template polystyrene microsphere, introduces sulfonic acid groups on the surface of the polystyrene microsphere to improve the electronegativity of the surface of the microsphere and enhance the electrostatic interaction between metal cobalt ions and the microsphere, thereby ensuring the uniform growth of the zeolite imidazole ester metal organic framework material on the surface of the microsphere, and after the template is removed through high-temperature pyrolysis carbonization, the prepared catalyst with a hollow structure can better inherit the microsphere structure of the polystyrene template.
(3) The cobalt and nitrogen co-doped carbon oxygen reduction catalyst prepared by the invention has a hollow structure after the template is removed, has a large specific surface area and a micropore/mesopore hierarchical pore structure, can effectively promote the exposure of an active site and the mass transfer of reactants, and has oxygen reduction catalytic activity superior to that of commercial Pt/C.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a scanning electron micrograph of polystyrene microspheres subjected to sulfonation in example 1;
FIG. 2 is a scanning electron microscope image of sulfonated polystyrene microspheres of example 1 with zeolitic imidazolate framework materials grown on the surface;
FIG. 3 is a transmission electron micrograph of transition metal Co and N co-doped carbon in example 1;
FIG. 4 is a polarization plot of cobalt and nitrogen co-doped carbon and commercial 20% Pt/C prepared at different reaction times in example 1.
Detailed Description
The invention is further elucidated with reference to the figures and examples. It should be understood that these examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention.
Example 1:
the preparation method comprises the following steps of preparing a cobalt and nitrogen co-doped carbon oxygen reduction catalyst by taking sulfonated polystyrene microspheres with zeolite imidazole ester framework compound materials (ZIF-67) growing on the surfaces as precursors through high-temperature pyrolysis carbonization, wherein the preparation method comprises the following steps:
washing a styrene monomer and a divinyl benzene monomer by using a sodium hydroxide solution with the mass fraction of 10%, and washing the styrene to be neutral by using deionized water; dissolving 0.7 g of cross-linking agent divinylbenzene in 120 mL of ultrapure water, stirring uniformly, adding 14 g of styrene, heating and reacting for 1 h under an inert atmosphere, dissolving 0.03 g of potassium persulfate in 10 mL of deionized water, adding into a reaction system, and continuing to react for 10 h; and adding a saturated NaCl solution into the reaction product, and performing suction filtration and drying on the precipitate to obtain the polystyrene microsphere. 1.70 g of polystyrene microsphere template and 60 mL of concentrated sulfuric acid are mixed into a beaker, and the polystyrene microspheres are uniformly dispersed by stirring or ultrasonic. And then stirring for 9 hours at the constant temperature of 40 ℃, centrifugally separating the reacted product, discarding unreacted concentrated sulfuric acid, repeatedly washing and separating the upper-layer product with excessive ethanol for 3-5 times, and drying the product in a vacuum drying oven.
Weighing 90 mg of sulfonated polystyrene microspheres, dissolving in 60 mL of methanol, performing ultrasonic treatment until the sulfonated polystyrene microspheres are uniformly dispersed, weighing 174 mg of cobalt nitrate hexahydrate, dissolving in 10 mL of methanol, weighing 492 mg of 2-methylimidazole, dissolving in 10 mL of methanol (the molar ratio of metal salt to 2-methylimidazole is 1: 10), performing ultrasonic treatment until the cobalt solution is dissolved, pouring the cobalt solution into the polystyrene microsphere emulsion, stirring by utilizing a magneton, slowly pouring the 2-methylimidazole solution into the sulfonated polystyrene microsphere emulsion, and continuously stirring and reacting for 14 hours at room temperature. And carrying out suction filtration on the obtained solution and drying. Placing appropriate amount of precursor in a tube furnace, vacuumizing to remove air, introducing argon gas for protection, and keeping at 5 deg.C for min -1 Heating to 700 ℃, keeping the temperature for 2h after heating, preparing the transition metal cobalt and nitrogen co-doped carbon catalyst, grinding the catalyst and filling the ground catalyst into a sample bottle.
Scanning electron microscope analysis and transmission electron microscope analysis are carried out on the precursor obtained in the embodiment, the prepared sulfonated polystyrene is spherical, the diameter is about 500 nm (figure 1), and the morphology of the sulfonated polystyrene template microsphere is still maintained after the ZIF-67 crystal grows (figure 2). The preparation of the cobalt and nitrogen co-doped carbon catalyst by pyrolysis and carbonization inherits the spherical shape of the precursor (figure 3). The oxygen reduction performance test (figure 4) shows that the catalyst has electrocatalytic activity superior to commercial 20% Pt/C.
Example 2
The operating conditions were the same as in example 1, except that the reaction time was increased to 18 h during the precursor preparation. The oxygen reduction performance test (figure 4) of the catalyst prepared by pyrolysis carbonization shows that the catalyst still shows excellent oxygen reduction catalytic activity.
Example 3
The operating conditions were the same as in example 1, except that the reaction time was increased to 22 h during the precursor preparation. The oxygen reduction performance test (figure 4) of the catalyst prepared by pyrolysis carbonization shows that the catalyst still shows excellent oxygen reduction catalytic activity.
Example 4
The operation conditions are the same as example 1, except that in the precursor preparation process, the molar ratio of the metal salt to the 2-methylimidazole is 1:20, and the prepared metal cobalt and nitrogen co-doped carbon catalyst still better maintains the microsphere morphology of the precursor.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst with a hollow structure is characterized by being prepared by the following preparation method:
(1) preparing polystyrene microspheres: washing a styrene monomer and a divinyl benzene monomer by adopting a sodium hydroxide solution with the mass fraction of 10%, and then washing the styrene monomer to be neutral by using deionized water; uniformly stirring water and a crosslinking agent divinylbenzene monomer, adding a styrene monomer, heating and reacting for 1-2 hours in an inert atmosphere, and adding a deionized water solution dissolved with potassium persulfate to continue the reaction; adding saturated NaCl solution into the reaction product, and performing suction filtration and drying on the precipitate to obtain polystyrene microspheres;
(2) preparing sulfonated polystyrene microsphere emulsion: mixing and stirring template polystyrene microspheres and concentrated sulfuric acid, centrifugally separating a product after reaction, washing the product with ethanol, and drying the product to prepare sulfonated polystyrene microspheres, dissolving the sulfonated polystyrene microspheres in an organic solvent, and uniformly dispersing the sulfonated polystyrene microspheres to obtain sulfonated polystyrene microsphere emulsion;
(3) preparing a precursor: respectively dissolving soluble salt of cobalt and an organic ligand in an organic solvent, and preparing polystyrene microspheres with the surface growth of the zeolite imidazolate metal organic framework material under the stirring condition;
(4) and (3) pyrolysis carbonization process: subjecting the precursor prepared in (3) to inert atmosphere at 1-10 deg.C for min -1 Heating to 600-900 deg.c and maintaining for 1-3 hr to obtain transition metal Co and N codoped carbon-oxygen reducing catalyst;
in the step (2), the organic solvent is one or more of methanol, ethanol and propylene glycol; the sulfonation temperature is 30-50 ℃, the reaction time is 8-10 h, the sulfonation solution is 98% concentrated sulfuric acid solution, and the mass ratio of the polystyrene microspheres to the concentrated sulfuric acid is 0.01-0.02;
the precursor of the catalyst is obtained by taking sulfonated polystyrene microspheres as a template and self-assembling a metal cobalt source and a nitrogen-containing organic ligand on the surfaces of the polystyrene microspheres, in the step (3), firstly, a cobalt solution is poured into the polystyrene microsphere emulsion in the step (2), and then, a solution containing the organic ligand is slowly poured into the polystyrene microsphere emulsion; the molar ratio of the soluble salt of the cobalt to the organic ligand is 0.05-0.25, and the reaction time is 14-22 h; the mass ratio of the cobalt salt to the polystyrene microspheres is 1.5-2.5;
the nitrogenous organic ligand is one or more of 2-methylimidazole, benzimidazole, imidazole and 2-imidazoline thioketone; the soluble salt of cobalt is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate.
2. The catalyst according to claim 1, wherein the transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst is prepared by pyrolysis and carbonization in an inert atmosphere, and in the step (4), the inert atmosphere is argon or nitrogen, and the holding time is 2-3 h.
3. The catalyst of claim 1 or 2 for use in a cathode oxygen reduction reaction of an alkaline fuel cell.
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| CN112509823B (en) * | 2020-12-22 | 2022-02-15 | 上海第二工业大学 | Hollow carbon microsphere supercapacitor electrode material and solvent-free preparation method thereof |
| CN112820886B (en) * | 2020-12-29 | 2023-05-26 | 北京化工大学 | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof |
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| CN113908874A (en) * | 2021-09-30 | 2022-01-11 | 华中科技大学 | Nitrogen-rich porous composite carbon material, and preparation method and application thereof |
| CN114188557B (en) * | 2021-10-29 | 2023-03-31 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN114497576A (en) * | 2022-01-19 | 2022-05-13 | 佛山仙湖实验室 | Low-cost ordered porous oxygen reduction catalyst and preparation method thereof |
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| CN114914460B (en) * | 2022-05-17 | 2023-09-01 | 深圳大学 | Dual-function catalytic material and preparation method and application thereof |
| CN115124020A (en) * | 2022-06-22 | 2022-09-30 | 江南大学 | Boron-nitrogen co-doped carbon material with hierarchical holes and preparation method and application thereof |
| CN115910623B (en) * | 2022-10-09 | 2023-10-27 | 黑龙江东方学院 | Cobalt nanoparticle/nitrogen-doped carbon porous sphere middle sphere composite material and preparation method and application thereof |
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