CN110280288B - Preparation method of transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst - Google Patents

Preparation method of transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst Download PDF

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CN110280288B
CN110280288B CN201910600752.4A CN201910600752A CN110280288B CN 110280288 B CN110280288 B CN 110280288B CN 201910600752 A CN201910600752 A CN 201910600752A CN 110280288 B CN110280288 B CN 110280288B
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cobalt
nitrogen
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CN110280288A (en
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王瀛
胡天军
胡琳果
袁宏杰
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Shaanxi Normal University
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Abstract

The invention discloses a preparation method of a transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, wherein transition metal in the catalyst comprises silver, cobalt and iron, and the molar ratio of the silver, the cobalt and the iron in the catalyst is 1 (8-12) to (5-9). The transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is prepared by a low-cost complexing method of a complexing agent and metal ions, has the characteristics of low cost and simplicity in operation and synthesis, does not need to add a metal reducing agent or independently add a nitrogen doping agent, can enable doping elements to be uniformly distributed, has high doping agent content on the surface of the catalyst, can effectively avoid the problems of metal particle agglomeration and the like, and improves the catalytic performance. The catalyst has high ORR and OER catalytic activity and stability in an alkaline solution, has good methanol resistance, and shows good catalytic performance when being applied to a zinc-air battery.

Description

Preparation method of transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst
Technical Field
The invention belongs to the technical field of non-noble metal catalysts, and particularly relates to a preparation method of a transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst.
Background
With the increasing energy crisis and the increasing degree of ecological damage, fuel cells, metal air cells and water electrolysis technologies are considered as effective clean energy storage devices replacing fossil fuels. Oxidation-Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) are the most critical reactions in electrochemical energy storage devices. The bifunctional catalyst with high catalytic activity for the two reactions of ORR and OER plays an important role in the technical field of renewable energy sources. Currently, noble metals (such as platinum, ruthenium, and iridium) and their alloys exhibit excellent electrochemical performance for both reactions. However, these precious metals have limited resources and high prices, and face the problem of excessive cost in commercialization, which limits their commercial application in energy storage devices.
With the development of research, a non-noble metal catalyst (transition metal-nitrogen doped carbon material, M-N-C) with application potential, which is synthesized from a precursor containing nitrogen, carbon and transition metal (Co, Fe, Mn, Ni, etc.), has received great attention due to its abundant resources and low price. M-N-C originated in the 60's of the 20 th century and was derived from macrocyclic complexes of transition metals (phthalocyanines and porphyrins). M-N-C catalysts exhibit good ORR performance in both basic and acidic media and are therefore widely studied. Although M-N-C exhibits highly selective catalytic activity, its conventional synthesis method generally involves complicated or multi-step operation techniques and addition of a metal reducing agent or addition of a nitrogen dopant, resulting in problems such as non-uniformity of distribution of doping elements, low content of dopant on the surface of the catalyst, and agglomeration of metal particles.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation dual-function catalyst, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation dual-function catalyst is prepared by a low-cost complexing agent-potassium ferricyanide and metal ion complexing method, the operation steps are simple, and a metal reducing agent is not required to be added or a nitrogen doping agent is not required to be added independently, so that the doping elements can be uniformly distributed, the doping agent content on the surface of the catalyst is high, the problems of metal particle agglomeration and the like can be effectively avoided, and the catalytic performance of the prepared transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation dual-function catalyst is improved.
The invention provides a transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, wherein transition metal in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst comprises silver, cobalt and iron, and the molar ratio of the silver, the cobalt and the iron in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is 1 (8-12) to (5-9).
In one embodiment, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution bifunctional catalyst is used for electrocatalytic oxygen reduction/oxygen evolution reaction.
The invention also provides a preparation method of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, which comprises the following steps:
mixing cobalt salt, a surfactant and deionized water to prepare a cobalt salt solution;
mixing an iron salt aqueous solution with the cobalt salt solution under the condition of stirring, and stirring and reacting for 0.5-1.0 h to prepare a first mixed solution, wherein the iron salt aqueous solution is a potassium ferricyanide aqueous solution;
mixing the silver salt aqueous solution with the first mixed solution under the condition of stirring, and stirring and reacting for 10.0-14.0 h to prepare a second mixed solution;
filtering the second mixed solution, washing filter residues, and drying at 70-90 ℃ for 10.0-14.0 h to obtain a catalyst precursor;
and roasting the catalyst for 1.0-3.0 h at 500-900 ℃ in an inert atmosphere to prepare the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst.
In one embodiment, the surfactant comprises any one or more of sodium lauryl sulfate, sodium citrate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
In one embodiment, in the cobalt salt solution, the molar ratio of the cobalt salt to the surfactant is 1: (1-10).
In one embodiment, the molar ratio of the silver salt aqueous solution, the cobalt salt solution and the iron salt aqueous solution added in each step is Ag+：Co2+：Fe3+The compositions are 1 (8-12) and 5-9.
In one embodiment, the cobalt salt is any one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate and cobalt chloride; the silver salt is silver nitrate.
In one embodiment, the molar concentration of the iron salt aqueous solution is 0.005 mol/L-0.015 mol/L.
In one embodiment, in the step of calcining the catalyst at 500-900 ℃ for 1-3 h in an inert atmosphere, the catalyst is heated from room temperature to 500-900 ℃ at a heating rate of 0.5-10.0 ℃/min in the inert atmosphere, and then is calcined for 1.0-3.0 h at 500-900 ℃.
In one embodiment, an aqueous iron salt solution is mixed with the cobalt salt solution under stirring to add the aqueous iron salt solution dropwise to the cobalt salt solution under stirring;
mixing the silver salt aqueous solution with the first mixed solution under stirring conditions to dropwise add the silver salt aqueous solution into the first mixed solution under stirring conditions.
The transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is prepared by a low-cost complexing agent-potassium ferricyanide and metal ion complexing method, has the characteristics of low cost and easiness in synthesis, does not need an additional metal reducing agent or a separate nitrogen doping agent, can ensure that doping elements are uniformly distributed, the content of the doping agent on the surface of the catalyst is high, and the problems of metal particle agglomeration and the like can be effectively avoided, so that the catalytic performance of the prepared transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is improvedAnd (4) performance is improved. The catalyst shows higher ORR and OER catalytic activity and stability in an alkaline solution, has better methanol resistance, and shows better catalytic performance when being applied to a zinc-air battery; further research proves that the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst has the advantages that several unrelated metal atoms with similar electronic structures are combined in crystal lattices, the electronic structure and geometric atom rearrangement of the catalyst are optimized, and the molecular O is reduced2The transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst obtained by introducing multi-metal into a nitrogen-doped carbon material and roasting at different temperatures has catalytic performance close to that of commercial Pt/C.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
FIG. 1 is an X-ray diffraction (XRD) pattern of the catalysts obtained in examples 1, 2 and 3;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the catalyst prepared in example 1;
FIG. 3 is a linear voltammogram of the catalysts prepared in examples 1, 2, and 3 and commercial Pt/C;
FIG. 4 shows the catalysts obtained in examples 1, 2 and 3 and RuO2Oxygen evolution polarization diagram of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The preparation method of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst provided by the embodiment of the invention comprises the following steps:
mixing cobalt salt, a surfactant and deionized water to prepare a cobalt salt solution;
mixing an iron salt aqueous solution with the cobalt salt solution under the condition of stirring, and stirring for reaction for 0.5-1.0 h to prepare a first mixed solution, wherein the iron salt aqueous solution is a potassium ferricyanide aqueous solution;
mixing the silver salt aqueous solution with the first mixed solution under the condition of stirring, and stirring for reaction for 10.0-14.0 h to prepare a second mixed solution;
filtering the second mixed solution, washing filter residues, and drying at 70-90 ℃ for 10.0-14.0 h to obtain a catalyst precursor;
the catalyst is roasted for 1.0 h-3.0 h at 500-900 ℃ in inert atmosphere to prepare the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation dual-function catalyst.
According to the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is prepared by a low-cost complexing agent-potassium ferricyanide and metal ion complexing method, and the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst has the characteristics of low cost and easiness in synthesis, does not need an additional metal reducing agent or a separate nitrogen doping agent, can ensure that doping elements are uniformly distributed, has high doping agent content on the surface of the catalyst, can effectively avoid the problems of metal particle agglomeration and the like, and accordingly improves the catalytic performance of the prepared transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst. The catalyst shows higher ORR and OER catalytic activity and stability in an alkaline solution, has better methanol resistance, and shows better catalytic performance when being applied to a zinc-air battery; further research proves that the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst has the advantages that several irrelevant metal atoms with similar electronic structures are combined in crystal lattices, the electronic structure and geometric atom rearrangement of the catalyst are optimized, the binding energy with molecular O2 is reduced, the electrocatalytic activity of the catalyst is improved, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst obtained by introducing multiple metals into a nitrogen-doped carbon material and roasting at different temperatures is close to that of commercial Pt/C, the stability and the methanol interference resistance are superior to those of the commercial Pt/C catalyst, and the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst has excellent application prospects in the field of new energy.
The transition metal in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst prepared by the method simultaneously contains silver, cobalt and iron, the molar ratio of silver, cobalt and iron in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is 1 (8-12) to (5-9), and the content of effective components is greatly improved compared with that of the transition metal-nitrogen doped carbon material prepared by the existing method.
Referring to the attached drawings 1 and 2, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst prepared by the preparation method of the present invention contains phases of Ag and CoFe, and thus can synergistically exert a catalytic effect; the microstructure of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is a core-shell structure, doping elements are uniformly distributed on the surface of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, and the particle size of the catalyst is nano-scale, so that the catalytic performance of the catalyst can be further effectively improved. As shown in fig. 3 and fig. 4, experiments prove that, compared to the transition metal-nitrogen Co-doped carbon material oxygen reduction/oxygen evolution bifunctional catalyst containing no Ag or no Co, the transition metal-nitrogen Co-doped carbon material oxygen reduction/oxygen evolution bifunctional catalyst containing three elements of silver, cobalt and iron prepared by the present invention has excellent catalytic activity; in addition, compared with the commercial product Pt/C, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution bifunctional catalyst has basically equivalent catalytic activity, but the preparation cost is greatly reduced.
The transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst disclosed by the invention can reduce the cost while maximally realizing the catalytic performance based on the composition and structural characteristics of the catalyst, and has extremely high commercial application value.
Further optionally, the molar ratio of silver, cobalt and iron in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is 1 (9-11): 6-8, and more preferably, the molar ratio of silver, cobalt and iron in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is 1:10: 7.
As an alternative embodiment, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution double-function catalyst is used for electrocatalytic oxygen reduction/oxygen evolution reaction.
In the preparation of the cobalt salt solution, a certain amount of surfactant is added, so that the complex reaction of iron salt and cobalt salt can be facilitated, the reaction is more stable, and the formed product is more uniform in components, so that the performance of the catalyst is further improved. Alternatively, the surfactant may be any one or more of sodium lauryl sulfate, sodium citrate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
As an alternative embodiment, the molar ratio of cobalt salt to said surfactant is 1: (1-10), preferably, the molar ratio of the cobalt salt to the surfactant is 1: (4-7).
Optionally, the cobalt salt in the cobalt salt solution is derived from any one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate and cobalt chloride; optionally, the source of silver salt in the aqueous silver salt solution is silver nitrate.
As an alternative embodiment, the molarity of the aqueous solution of the iron salt is 0.005mol/L to 0.015mol/L, preferably the molarity of the aqueous solution of the iron salt is 0.008mol/L to 0.012 mol/L. The molarity of the ferric salt aqueous solution is crucial to the generation of the product as the source of three important components of carbon, nitrogen and iron in the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst, and an effective complex product cannot be generated if the molarity of the ferric salt aqueous solution is too high or too low, so that the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst with good catalytic activity is prepared.
As an optional embodiment, in the step of calcining the catalyst at 500-900 ℃ for 1-3 h in an inert atmosphere, the catalyst is heated from room temperature to 500-900 ℃ at a heating rate of 0.5-10.0 ℃/min in the inert atmosphere, and then is calcined at 500-900 ℃ for 1.0-3.0 h.
As an alternative embodiment, the ferric salt aqueous solution and the cobalt salt solution are mixed under stirring, and the ferric salt aqueous solution is added into the cobalt salt solution dropwise under stirring; the silver salt aqueous solution and the first mixed solution are mixed under stirring, and the silver salt aqueous solution is added dropwise into the first mixed solution under stirring.
Example 1
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 70mL of ferric salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 2
Dissolving 0.01mol of cobalt nitrate and 0.01mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 70mL of ferric salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 500 ℃ at the speed of 0.5 ℃/min under the atmosphere of inert gas, roasting at 500 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 3
Dissolving 0.01mol of cobalt nitrate and 0.01mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 70mL of ferric salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 600 ℃ at the speed of 0.5 ℃/min under the inert gas atmosphere, roasting at 600 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 4
Dissolving 0.01mol of cobalt nitrate and 0.10mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 70mL of ferric salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ at the speed of 10.0 ℃/min under the atmosphere of inert gas, roasting at 800 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 5
Dissolving 0.01mol of cobalt nitrate and 0.01mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.005mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 140mL of iron salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 6
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 50mL of iron salt aqueous solution is dropwise added into 80mL of cobalt salt solution, stirring reaction is continued for 30min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 10h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 800 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 7
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 90mL of iron salt aqueous solution is dropwise added into 120mL of cobalt salt solution, stirring reaction is continued for 60min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 14h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out at 80 ℃ for 12h, so that the catalyst precursor is prepared.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 900 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 900 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 8
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.015mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 47mL of ferric salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 900 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 900 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 9
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 60mL of iron salt aqueous solution is dropwise added into 90mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 10
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 80mL of ferric salt aqueous solution is dropwise added into 110mL of cobalt salt solution, stirring reaction is continued for 45min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 11
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 50mL of iron salt aqueous solution is dropwise added into 120mL of cobalt salt solution, stirring reaction is continued for 60min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
Example 12
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 90mL of iron salt aqueous solution is dropwise added into 80mL of cobalt salt solution, stirring reaction is continued for 60min, 10mL of silver salt solution is dropwise added into the mixed solution under the condition of stirring, stirring reaction is continued for 12h, filtering is carried out, the obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the double-function catalyst for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material, which is marked as Ag-CoFe @ N-C.
The catalysts prepared in examples 1 to 11 were deposited on rotating disk electrodes, respectively, at a loading of 200. mu.g/cm2The electrochemical device is composed of a glass battery, an alkaline electrolyte, a Pt wire auxiliary electrode and an Hg/HgO reference electrode, and a potentiostat is used for test and determination. The activity of the oxygen reduction/oxygen evolution reaction was measured as an electrode potential at a given current density, and the results are shown in Table 1.
TABLE 1 catalytic Activity of transition metal-nitrogen co-doped carbon Material oxygen reduction/oxygen evolution bifunctional catalyst
Catalyst and process for preparing same Ej＝3(V) Ej＝10(V) ΔE(V)
Example 1 -0.09 0.69 0.78
Example 2 -0.12 0.72 0.84
Example 3 -0.15 0.74 0.89
Example 4 -0.17 0.73 0.90
Example 5 -0.14 0.77 0.91
Example 6 -0.20 0.71 0.91
Example 7 -0.18 0.74 0.92
Example 8 -0.11 0.78 0.89
Example 9 -0.14 0.77 0.91
Example 10 -0.18 0.72 0.90
Example 11 -0.13 0.78 0.91
Example 12 -0.16 0.73 0.89
Comparative example 1
Dissolving 0.01mol of cobalt nitrate and 0.05mol of surfactant with deionized water to a constant volume of 1000mL to prepare a cobalt salt solution; 0.01mol of potassium ferricyanide is dissolved with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution.
Under the condition of magnetic stirring, 70mL of iron salt aqueous solution is dropwise added into 100mL of cobalt salt solution, stirring reaction is continued for 45min, filtering is carried out, obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst which is marked as CoFe @ N-C.
Comparative example 2
Dissolving 0.01mol of potassium ferricyanide with deionized water to a constant volume of 1000mL to prepare an iron salt aqueous solution; dissolving 0.01mol of silver nitrate in deionized water to a constant volume of 1000mL to prepare silver salt solution.
Under the condition of magnetic stirring, 10mL of silver salt solution is dropwise added into 70mL of iron salt aqueous solution, stirring reaction is continued for 12h, filtering is carried out, obtained filter residue is sequentially washed by ethanol and deionized water, and drying is carried out for 12h at 80 ℃ to obtain the catalyst precursor.
Grinding a catalyst precursor into powder, putting a certain amount of the catalyst precursor into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 700 ℃ at the speed of 5.0 ℃/min under the atmosphere of inert gas, roasting at 700 ℃ for 2.0h, and cooling to room temperature to obtain the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst which is marked as AgFe @ N-C.
Referring to fig. 1, which shows XRD diffractograms of the three transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution bifunctional catalysts Ag-CoFe @ N-C, CoFe @ N-C, AgFe @ N-C respectively prepared in example 1 and comparative examples 1 and 2 of the present invention, it can be seen that three diffraction peaks at 38.1 ° and 77.5 ° 81.5 ° are characteristic peaks of Ag; the three diffraction peaks at 44.9 °, 65.3 °, and 82.7 ° are characteristic peaks of CoFe. Thus, the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst Ag-CoFe @ N-C prepared in example 1 of the application contains Ag and CoFe phases.
As shown in fig. 2, it can be seen that the microstructure formed by the dual-functional catalyst Ag-CoFe @ N-C for oxygen reduction/oxygen precipitation of the transition metal-nitrogen co-doped carbon material prepared in example 1 of the present invention is a core-shell structure, the doping elements are uniformly distributed on the surface, and the particle size of the catalyst is nanometer, so that the catalytic performance of the catalyst can be effectively improved.
Referring to fig. 3, an electrochemical workstation is adopted to test the electrochemical performance of the prepared transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution dual-function catalyst, and as can be seen from fig. 3, the catalytic activity of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution dual-function catalyst Ag-CoFe @ N-C prepared in example 1 of the present invention is substantially equal to that of a commercial product Pt/C, and the half-wave potential of the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen evolution dual-function catalyst Ag-CoFe @ N-C is only 42mV different from that of the commercial product Pt/C. And the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst CoFe @ N-C, AgFe @ N-C worthy of comparative examples 1 and 2 has poor catalytic activity due to the property limitation.
Continuing with FIG. 4, it can be seen that at a current density of 10mA cm-2In the invention, the prepared transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst Ag-CoFe @ N-C has a higher RuO content than that of RuO2A small overpotential.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. A preparation method of a transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst is characterized by comprising the following steps:
mixing cobalt salt, a surfactant and deionized water to prepare a cobalt salt solution;
mixing an iron salt aqueous solution with the cobalt salt solution under the condition of stirring, and stirring and reacting for 0.5-1.0 h to prepare a first mixed solution, wherein the iron salt aqueous solution is a potassium ferricyanide aqueous solution;
mixing a silver salt aqueous solution with the first mixed solution under the condition of stirring, and stirring and reacting for 10.0-14.0 h to prepare a second mixed solution;
filtering the second mixed solution, washing filter residues, and drying at 70-90 ℃ for 10.0-14.0 h to obtain a catalyst precursor;
roasting the catalyst for 1.0-3.0 h at 500-900 ℃ in an inert atmosphere to prepare the transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation dual-function catalyst;
the molar concentration of the ferric salt water solution is 0.005-0.015 mol/L;
the surfactant comprises one or more of lauryl sodium sulfate, sodium citrate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer;
the molar ratio of the silver salt aqueous solution, the cobalt salt aqueous solution and the ferric salt aqueous solution added in each step is Ag+：Co2+：Fe3+The compositions are 1 (8-12) and 5-9.
2. The method according to claim 1, wherein the molar ratio of the cobalt salt to the surfactant in the cobalt salt solution is 1: (1-10).
3. The preparation method according to claim 1, wherein the cobalt salt is any one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate and cobalt chloride; the silver salt is silver nitrate.
4. The preparation method of claim 1, wherein in the step of calcining the catalyst at 500-900 ℃ for 1-3 h in an inert atmosphere, the catalyst is heated from room temperature to 500-900 ℃ at a heating rate of 0.5-10.0 ℃/min in the inert atmosphere, and then is calcined at 500-900 ℃ for 1.0-3.0 h.
5. The method according to any one of claims 1 to 4, wherein an aqueous iron salt solution is mixed with the cobalt salt solution under stirring to add the aqueous iron salt solution dropwise to the cobalt salt solution under stirring;
mixing the silver salt aqueous solution with the first mixed solution under stirring conditions to dropwise add the silver salt aqueous solution into the first mixed solution under stirring conditions.
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CN112768706B (en) * 2019-11-05 2022-01-28 中国科学院大连化学物理研究所 Core-shell catalyst, preparation method thereof and application of core-shell catalyst in rechargeable zinc-air battery
CN111001428B (en) * 2019-12-24 2021-05-14 山西大学 Metal-free carbon-based electrocatalyst, preparation method and application
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108011110A (en) * 2017-11-23 2018-05-08 华南理工大学 A kind of transition metal of high-specific surface area-nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application
CN108493461A (en) * 2018-05-08 2018-09-04 大连理工大学 A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles
CN108722460A (en) * 2018-04-08 2018-11-02 湖北大学 NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140045081A1 (en) * 2012-08-10 2014-02-13 Ph Matter, Llc Bifunctional electrode design and method of forming same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108011110A (en) * 2017-11-23 2018-05-08 华南理工大学 A kind of transition metal of high-specific surface area-nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application
CN108722460A (en) * 2018-04-08 2018-11-02 湖北大学 NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof
CN108493461A (en) * 2018-05-08 2018-09-04 大连理工大学 A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
In situ integration of Co Fe alloy nanoparticles with nitrogen-doped carbon nanotubes as advanced bifunctional cathode catalyst s for Zn–air batteries;Pingwei Cai et al.;《Nanoscale》;20161110;第8卷;摘要 *
One-pot synthesis of Ag-CoFe2O4/C as efficient catalyst for oxygen reduction in alkaline media;Ying Wang et al.;《International Journal of Hydrogen Energy》;20160617;第41卷;摘要 *
氮掺杂还原氧化石墨包覆金属钴复合材料的制备及其氧还原性能的研究;陈圈生等;《北京化工大学学报(自然科学版)》;20190520(第03期);第45-55页 *

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