CN115084556A - Nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-functional catalyst and preparation method thereof - Google Patents

Nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-functional catalyst and preparation method thereof Download PDF

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CN115084556A
CN115084556A CN202210802486.5A CN202210802486A CN115084556A CN 115084556 A CN115084556 A CN 115084556A CN 202210802486 A CN202210802486 A CN 202210802486A CN 115084556 A CN115084556 A CN 115084556A
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张海宁
谭时峰
程亚鹏
唐浩林
潘红飞
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Foshan Xianhu Laboratory
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Abstract

The invention belongs to the technical field of oxygen reduction and oxygen precipitation catalysts, and particularly discloses a nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst and a preparation method thereof. Firstly, carbonizing a carbon source and a nitrogen source at a certain temperature to prepare nitrogen-doped carbon; adding nitrogen-doped carbon into a mixed aqueous solution of an iron source, a cobalt source and a dispersing agent to prepare a precursor solution; drying the precursor solution to prepare a precursor; and finally, pyrolyzing the precursor at high temperature to prepare the nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst. The invention uniformly and stably loads iron and cobalt in nitrogen-doped carbon, adjusts the electronic state and electron transfer of the metal nitrogen-carbon active site, enables the catalyst to realize high-efficiency dual-function catalysis on oxygen reduction and oxygen precipitation, has better catalytic performance than commercial platinum-carbon catalysts and iridium oxide catalysts using noble metals, greatly reduces the preparation cost, and has wide application prospect.

Description

Nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-functional catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of oxygen reduction and oxygen precipitation catalysts, and particularly relates to a nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst and a preparation method thereof.
Background
With the growing demand for energy and the consumption of fossil fuels, intensive research has been conducted on renewable energy conversion and storage systems, such as fuel cells, metal air cells, and water electrolysis. Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) of the oxygen electrode play an important role in energy conversion and storage devices, where large overpotentials are required to overcome the complex and kinetically slow electron transfer process, which hinders the efficiency of the ORR and OER reactions. Therefore, the preparation of high efficiency catalysts to reduce the ORR and OER overpotentials and thereby improve energy conversion efficiency is the hot spot of current research.
To date, noble metal (Pt, Ir, Ru, etc.) based catalysts are still the major commercial catalysts, but the large-scale application of noble metal based catalysts is severely limited by their disadvantages of scarcity, stability, and cost. Furthermore, the performance of noble metal-based catalysts is closely related to the noble metal species, and the oxygen catalytic activity of different metals differs greatly, usually showing only selective OER or ORR activity. For example, Pt and its alloys are generally considered to be the most effective ORR catalysts, but have low catalytic activity for OER; ir catalysts are currently the most advanced single component OER catalysts, but have a lower ORR activity. In this case, the construction of a low-cost, highly active bifunctional catalyst is a major challenge.
In recent years, research on non-noble metal catalysts has been conducted, and since a high-efficiency oxygen reaction catalyst generally requires interaction with an oxygen reaction intermediate, it is likely that incorporation of a plurality of metal elements having different bonding actions into the catalyst will become a way of realizing a bifunctional catalyst. However, due to the complex composition, different metal elements and coordination environments, different active site designs and site electronic states, different material morphologies, etc., all of which affect the reaction mechanism, making the preparation of high performance multi-element catalysts challenging. In addition, agglomeration of metal nanoparticles during the catalytic process results in poor catalyst stability, which is also a serious problem. Therefore, there is a need to develop an optimized elemental mixture and structurally stable multi-element catalyst to achieve efficient bi-functional catalysis of oxygen electrode reactions.
Disclosure of Invention
Aiming at the defects of the existing non-noble metal oxygen reduction/oxygen precipitation dual-function catalyst, the invention provides the nitrogen-doped carbon supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-function catalyst and the preparation method thereof.
In order to solve the technical problem provided by the invention, the invention provides a preparation method of a nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst, which comprises the following steps:
1) mixing a carbon source and a nitrogen source, and grinding into powder to prepare a uniform carbon-nitrogen mixture;
2) carbonizing the nitrogen-carbon mixture, and grinding the obtained carbide into powder to obtain nitrogen-doped carbon;
3) uniformly mixing an iron source, a cobalt source and a dispersing agent in water, adding nitrogen-doped carbon, and uniformly mixing to prepare a precursor solution;
4) drying the precursor solution, and grinding the obtained solid into powder to prepare a precursor;
5) and pyrolyzing the precursor to obtain the nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst.
In the above scheme, the carbon source is glucose, and the nitrogen source is dicyandiamide.
In the scheme, the mass ratio of the carbon source to the nitrogen source is 1 (15-25).
In the scheme, the carbonization process in the step 2) comprises the steps of heating to 450-650 ℃ at the heating rate of 1-10 ℃/min under the protection of inert atmosphere, preserving heat for 0.5-3h, and then cooling to room temperature.
In the above scheme, the iron source is FeCl 2 ·2H 2 O、Fe(CH 3 COO) 2 ·4H 2 O、FeSO 4 ·7H 2 O, and the like.
In the above scheme, the cobalt source is CoCl 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Co(CH 3 COO) 2 ·4H 2 O、CoSO 4 ·7H 2 O, and the like.
In the scheme, the dispersing agent is one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, sodium dodecyl sulfate, polyacrylamide, sodium tripolyphosphate and the like.
In the scheme, the mass ratio of the carbon source to the cobalt source is (3-7):1, and the mass ratio of the cobalt source to the iron source is (0.5-2): 1.
In the scheme, the mass ratio of the dispersing agent to the carbon source is (1-3) to 1, and the mass-volume ratio of the dispersing agent to the water is 5mg (0.5-2) mL.
In the scheme, the drying process in the step 4) is to heat the precursor solution to 60-100 ℃, and dry the precursor solution while stirring at a stirring speed of 100-.
In the scheme, the pyrolysis process in the step 5) comprises the steps of heating to 800-1000 ℃ at a heating rate of 1-10 ℃/min under the protection of inert atmosphere, preserving heat for 1-3h, and then cooling to room temperature.
In the scheme, the grinding time in the step 1), the step 2) and the step 4) is 10-60min, and the particle size of the ground powder is less than or equal to 60 mu m.
The invention also provides a nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst which is prepared according to the scheme.
Compared with the prior art, the invention has the beneficial effects that:
1) on one hand, glucose and dicyandiamide are respectively used as a carbon source and a nitrogen source and are carbonized at a certain temperature to generate a plurality of layers of nano sheets containing a large number of lone-pair electron pairs, so that iron-cobalt metal ions in a solution can be effectively adsorbed, and subsequent metal ions are uniformly doped in a carbon framework and coated in a nitrogen-doped carbon layer; on the other hand, the dispersion degree of the iron-cobalt metal ions is further increased by adding the dispersing agent, the Ostwald curing process of the metal particles in the pyrolysis process is slowed down, and the size of the iron-cobalt nanoparticles is effectively controlled; therefore, the prepared catalyst has stable iron-cobalt load and smaller iron-cobalt nanoparticles, thereby having higher stability and catalytic activity.
2) According to the invention, by introducing ferrous iron, the formed iron nitrogen carbon active site is more beneficial to four electron transfer and has higher oxygen reduction (ORR) activity; then, by introducing cobalt, the electronic state of the metal nitrogen-carbon active site is adjusted by the nano alloy formed by iron and cobalt, so that stronger affinity is provided for adsorption of oxygen species, and the catalytic activity of Oxygen Evolution (OER) is improved; in addition, the nitrogen-doped carbon layer coated on the surface of the alloy further improves the exposed surface of active sites, electrons and mass transfer; through the comprehensive action, the prepared catalyst realizes high-efficiency dual-function catalysis on oxygen electrode reaction.
3) The preparation method is simple, the conventional non-noble metals such as iron, cobalt and the like are adopted, the prepared catalyst has better electrochemical performance than a commercial platinum-carbon catalyst and an iridium oxide catalyst which use noble metals, but the preparation cost is greatly reduced, and the preparation method has wide application prospect.
Drawings
FIG. 1 is an SEM image of a catalyst FeCo @ MNC prepared in example 1 of the present invention.
FIG. 2 is a TEM image of a catalyst FeCo @ MNC prepared according to example 1 of the present invention.
FIG. 3 is a HAADF diagram of the catalyst FeCo @ MNC prepared in example 1 of the present invention.
FIG. 4 shows the catalyst prepared in example 1 of the present inventionN of FeCo @ MNC 2 And (4) removing the attached drawing by adsorption.
FIG. 5 is a current-time curve of the catalyst FeCo @ MNC prepared in example 1 of the present invention measured in a 0.1mol/L KOH solution at 1600 rpm.
FIG. 6 shows the preparation of the catalyst FeCo @ MNC in 1mol/L KOH solution and 10mA/cm 2 Current-time curve measured at current density.
FIG. 7 shows the oxygen reduction LSV spectra of the catalyst FeCo @ MNC and the commercial Pt/C catalyst prepared in example 1 of the present invention in a 0.1mol/L KOH solution.
FIG. 8 is a polarization curve of the catalysts prepared in examples 1 and 2-3 of the present invention in a 0.1mol/L KOH solution.
FIG. 9 is a TEM image of the catalyst prepared in comparative example 1 of the present invention.
FIG. 10 is a TEM image of a catalyst prepared in comparative example 2 of the present invention.
FIG. 11 shows the catalysts prepared in example 1 and comparative examples 3 to 4 of the present invention and commercial IrO 2 The oxygen evolution LSV pattern of the catalyst in a 1mol/L KOH solution.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst comprises the following steps:
1) uniformly mixing 0.25g of glucose and 5g of dicyandiamide, and grinding for 30min to form powder with the particle size of less than or equal to 60 mu m to prepare a uniform carbon-nitrogen mixture;
2) placing the carbon-nitrogen mixture in an argon atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 2h for carbonization, cooling to room temperature, grinding the carbide for 30min to form powder with the particle size of less than or equal to 60 mu m, and preparing nitrogen-doped carbon;
3) 0.05g of Co (NO) 3 ) 2 ·6H 2 O、0.05g FeCl 2 ·2H 2 O and 0.5g of polyethylene oxide-polyUniformly mixing the propylene oxide-polyethylene oxide triblock copolymer in 100mL of water, adding the nitrogen-doped carbon obtained in the step 2), and uniformly mixing again to obtain a precursor solution;
4) heating the precursor solution to 95 ℃, stirring and drying at the speed of 300r/min until the water is completely evaporated to dryness, and grinding the obtained solid for 30min to form powder with the particle size of less than or equal to 60 mu m to obtain a precursor;
5) and (3) placing the precursor in an argon atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h for pyrolysis, and cooling to room temperature to obtain the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst which is recorded as FeCo @ MNC.
FIG. 1 is an SEM image of the catalyst FeCo @ MNC prepared in this example, and it can be seen that the catalyst exists mainly in a two-dimensional form and has a few carbon nanotubes.
FIG. 2 is a TEM image of FeCo @ MNC catalyst prepared in this example, and it can be seen that metal particles are uniformly dispersed in a two-dimensional thin sheet carbon material and form a carbon-coated alloy structure, iron and cobalt loading is stable, and the size of iron and cobalt nanoparticles is not more than 60 nm.
FIG. 3 is a graph of HAADF of the catalyst FeCo @ MNC prepared in this example, and it can be seen that no aggregation of metal particles is observed.
FIG. 4 shows N of FeCo @ MNC catalyst prepared in this example 2 The adsorption is removed from the figure, and the BET specific surface area is 300.6m 2 The catalyst has larger specific surface area and pore channel area.
FIG. 5 is a current-time curve of FeCo @ MNC catalyst prepared in this example measured in 0.1mol/L KOH solution at 1600rpm, from which it can be seen that 90.3% of current is still retained after 30000s of test, indicating that the catalyst has excellent oxygen reduction stability.
FIG. 6 shows the preparation of FeCo @ MNC catalyst in 1mol/L KOH solution at 10mA/cm 2 The current-time curve measured at the current density, as can be seen from the figure, remains 95 of the initial current after 10h of testing%, indicating that the catalyst has excellent oxygen evolution stability.
FIG. 7 is an oxygen reduction LSV spectrum of the catalysts FeCo @ MNC and commercial Pt/C catalyst prepared in this example in 0.1mol/L KOH solution, and it can be seen from the graph that the initial potentials of the FeCo @ MNC catalyst and the Pt/C catalyst are 0.996V and 0.913V respectively, the half-wave potentials are 0.878V and 0.830V respectively, and the FeCo @ MNC has more positive half-wave potential and initial potential, and exhibits more excellent electrochemical performance.
Examples 2 to 3
Examples 2-3 the other steps and parameters were the same as in example 1, except that: the pyrolysis temperature for example 2 was 800 ℃ and the pyrolysis temperature for example 3 was 1000 ℃.
Comparing example 1 and examples 2-3, it can be seen from fig. 8 that the 900 c pyrolyzed catalyst has the most positive half-wave potential and the best catalyst activity.
Example 4
1) Uniformly mixing 0.5g of glucose and 7.5g of dicyandiamide, and grinding for 30min to form powder with the particle size of less than or equal to 60 mu m to obtain a uniform carbon-nitrogen mixture;
2) placing the carbon-nitrogen mixture in a nitrogen atmosphere, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 3h for carbonization, cooling to room temperature, grinding the carbide for 30min to form powder with the particle size of less than or equal to 60 mu m, and preparing nitrogen-doped carbon;
3) 0.15g of Co (CH) 3 COO) 2 ·4H 2 O、0.15g Fe(CH 3 COO) 2 ·4H 2 Mixing O and 1.5g of sodium dodecyl sulfate in 500mL of water uniformly, adding the nitrogen-doped carbon obtained in the step 2), and mixing uniformly again to obtain a precursor solution;
4) heating the precursor solution to 90 ℃, stirring and drying at the speed of 400r/min until the water is completely evaporated to dryness, and grinding the obtained solid for 50min to form powder with the particle size of less than or equal to 60 mu m to obtain a precursor;
5) and (3) placing the precursor in an argon atmosphere, heating to 800 ℃ at the speed of 6 ℃/min, preserving the temperature for 3h for pyrolysis, and cooling to room temperature to obtain the nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst.
Example 5
1) Uniformly mixing 0.5g of glucose and 10g of dicyandiamide, and grinding for 30min to form powder with the particle size of less than or equal to 60 mu m to prepare a uniform carbon-nitrogen mixture;
2) placing the carbon-nitrogen mixture in a nitrogen atmosphere, heating to 500 ℃ at the speed of 3 ℃/min, preserving heat for 1h for carbonization, cooling to room temperature, grinding the carbide for 30min to form powder with the particle size of less than or equal to 60 mu m, and preparing nitrogen-doped carbon;
3) 0.08g of CoCl 2 ·6H 2 O、0.08g FeSO 4 ·7H 2 Mixing O and 0.5g of sodium tripolyphosphate in 80mL of water uniformly, adding the nitrogen-doped carbon in the step 2), and mixing uniformly again to prepare a precursor solution;
4) heating the precursor solution to 85 ℃, stirring and drying at the speed of 300r/min until the water is completely evaporated to dryness, and grinding the obtained solid for 20min to form powder with the particle size of less than or equal to 60 mu m to obtain a precursor;
5) and (3) placing the precursor in an argon atmosphere, heating to 900 ℃ at the speed of 4 ℃/min, preserving the heat for 1.5h for pyrolysis, and cooling to room temperature to obtain the nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst.
Comparative example 1
Comparative example 1 the other steps and parameters were the same as in example 1, except that: the nitrogen source is urea.
Fig. 9 is a TEM image of the catalyst prepared in this comparative example, and it can be seen from the image that the morphology of the catalyst using urea as a nitrogen source is in a lump form, a two-dimensional thin sheet carbon material and a carbon-coated alloy structure are not formed, and a metal aggregation phenomenon is significant.
Comparative example 2
Comparative example 2 the other steps and parameters were the same as in example 1, except that: no polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer was added.
FIG. 10 is a TEM image of the catalyst prepared in this comparative example, and it can be seen that metal agglomeration occurred without the addition of the dispersant.
Comparative examples 3 to 4
Comparative examples 3-4 the other steps and parameters were the same as in example 1, except that: comparative example 3 no iron source was added and the catalyst was reported as Co @ MNC; comparative example 4 no cobalt source was added and the catalyst was reported as Fe @ MNC.
FIG. 11 shows the catalysts prepared in example 1 and comparative examples 3 to 4 of the present invention and commercial IrO 2 The LSV patterns of the oxygen evolution of the catalysts in a 1mol/L KOH solution are shown in the figure, FeCo @ MNC, Co @ MNC, Fe @ MNC and commercial IrO 2 At 10mA/cm 2 The overpotential under the current density is 322mv, 362mv, 410mv and 335mv respectively, and the oxygen evolution catalytic performance of Co @ MNC and Fe @ MNC is inferior to that of commercial IrO 2 And the oxygen evolution catalytic performance of FeCo @ MNC is superior to that of commercial IrO 2 。
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessarily exhaustive of all embodiments, and are therefore intended to be within the scope of the invention.

Claims (10)

1. A preparation method of a nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst is characterized by comprising the following steps:
1) mixing a carbon source and a nitrogen source, and grinding into powder to prepare a uniform carbon-nitrogen mixture; the carbon source is glucose, and the nitrogen source is dicyandiamide;
2) placing the carbon-nitrogen mixture in an inert atmosphere, heating to 450-650 ℃ for carbonization, and grinding the obtained carbide into powder to obtain nitrogen-doped carbon;
3) uniformly mixing an iron source, a cobalt source and a dispersing agent in water, adding nitrogen-doped carbon, and uniformly mixing to prepare a precursor solution;
4) drying the precursor solution under the condition of stirring, and grinding the obtained solid into powder to prepare a precursor;
5) and (3) placing the precursor in an inert atmosphere, heating to 800-1000 ℃ for pyrolysis, and preparing the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-function catalyst.
2. The method for preparing the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen evolution bifunctional catalyst according to claim 1, wherein the iron source is FeCl 2 ·2H 2 O、Fe(CH 3 COO) 2 ·4H 2 O、FeSO 4 ·7H 2 And O is one of the compounds.
3. The method for preparing the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen evolution bifunctional catalyst according to claim 1, wherein the cobalt source is CoCl 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Co(CH 3 COO) 2 ·4H 2 O、CoSO 4 ·7H 2 And O is one of the compounds.
4. The method for preparing the nitrogen-doped carbon-supported iron cobalt nanoparticle catalyst with the double functions of oxygen reduction and oxygen precipitation according to claim 1, wherein the dispersing agent is one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, sodium dodecyl sulfate, polyacrylamide and sodium tripolyphosphate.
5. The preparation method of the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst as claimed in claim 1, wherein the mass ratio of the carbon source to the nitrogen source is 1 (15-25), the mass ratio of the carbon source to the cobalt source is (3-7):1, and the mass ratio of the cobalt source to the iron source is (0.5-2): 1.
6. The preparation method of the nitrogen-doped carbon-supported iron cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst as claimed in claim 1, wherein the mass ratio of the dispersant to the carbon source is (1-3):1, and the mass-to-volume ratio of the dispersant to water is 5mg (0.5-2) mL.
7. The preparation method of the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst according to claim 1, wherein the temperature rise rate of the carbonization in the step 2) is 1-10 ℃/min, and the heat preservation time is 0.5-3 h; the heating rate of the pyrolysis in the step 5) is 1-10 ℃/min, and the heat preservation time is 1-3 h.
8. The method for preparing the nitrogen-doped carbon-supported iron cobalt nanoparticle oxygen reduction/oxygen evolution bifunctional catalyst as claimed in claim 1, wherein the drying temperature in the step 4) is 60-100 ℃, and the stirring speed during drying is 100-500 r/min.
9. The preparation method of the nitrogen-doped carbon-supported iron-cobalt nanoparticle oxygen reduction/oxygen precipitation bifunctional catalyst as claimed in claim 1, wherein the grinding time in the steps 1), 2) and 4) is 10-60min, and the particle size of the ground powder is less than or equal to 60 μm.
10. An oxygen reduction/oxygen evolution bifunctional catalyst of nitrogen doped carbon supported iron cobalt nanoparticles prepared by the method of any one of claims 1-9.
CN202210802486.5A 2022-07-07 2022-07-07 Nitrogen-doped carbon-loaded iron-cobalt nanoparticle oxygen reduction/oxygen precipitation dual-functional catalyst and preparation method thereof Pending CN115084556A (en)

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