CN114335566A - Ni/Co-N doped porous carbon-oxygen reduction catalyst and preparation method thereof - Google Patents
Ni/Co-N doped porous carbon-oxygen reduction catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Ni/Co-N doped porous carbon-oxygen reduction catalyst and a preparation method thereof2The ball is used as a template, a second metal Co is added into a reaction system and compounded with metal Ni to form a more efficient Ni/Co electrocatalytic active center, and the catalytic reaction capability of the material is further enhanced through the synergistic effect of the two. Then growing carbon nano tube in situ and removing SiO2After a series of steps such as template, the Ni/Co-N doped three-dimensional porous carbon structure is successfully constructed, and the catalytic activity of the material is further improved.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a Ni/Co-N doped porous carbon-oxygen reduction catalyst and a preparation method thereof.
Background
To achieve the goals of carbon peaking and carbon neutralization, the energy structure must be actively tuned. The hydrogen energy is a green pollution-free zero-emission energy form, and has great application potential and development prospect. The fuel cell is a novel energy conversion and storage device for generating electricity by using hydrogen energy, and the Oxygen Reduction Reaction (ORR) rate of the cathode side of the fuel cell is slow, so that the practical application of the fuel cell is greatly limited. Therefore, the use of catalysts to accelerate oxygen reduction is a viable and effective method, and precious metal-based materials, represented by platinum carbon, now account for the major share of commercial ORR catalysts. The development of the non-noble metal-based efficient ORR catalyst is significant in reducing the cost of the fuel cell. However, the activity of the single metal base oxygen reduction catalyst is limited and cannot reach the performance index of the fuel cell. Ni and Co belong to the VIII family element in the fourth period, have less than filled 3d orbit, have the coordination ability with atoms such as N, and can be used as the catalytic site of oxygen reduction reaction to play a role. Therefore, the design and preparation of the Ni and Co bimetal supported high-efficiency ORR catalyst have important significance for the research and development of non-noble metal catalysts.
Disclosure of Invention
In order to solve the existing problems, the invention provides a Ni/Co-N doped porous carbon-oxygen reduction catalyst and a preparation method thereof, wherein a Ni-based metal organic framework (Ni-MOF) is adopted as a matrix material, and SiO is introduced into a system by adding tetraethyl orthosilicate2The ball is used as a template, a second metal Co is added into a reaction system and compounded with metal Ni to form a more efficient Ni/Co electrocatalytic active center, and the catalytic reaction capability of the material is further enhanced through the synergistic effect of the two. Then growing carbon nano tube in situ and removing SiO2And after a series of steps such as template and the like, the Ni/Co-N doped three-dimensional porous carbon structure is successfully constructed, and the method is suitable for popularization and application.
The technical scheme adopted by the invention is as follows: a preparation method of a Ni/Co-N doped porous carbon-oxygen reduction catalyst comprises the following steps:
step one, dissolving nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane in a N, N-dimethylformamide DMF solution;
placing the mixed solution into a reaction kettle, reacting in an oven with the reaction temperature of 120-130 ℃, cleaning the obtained green powder with a proper amount of DMF solution, and drying to obtain a Ni metal organic framework material (Ni-MOF);
dissolving Ni-MOF in absolute ethyl alcohol, performing ultrasonic treatment for 25-35 min, sequentially adding Cetyl Trimethyl Ammonium Bromide (CTAB), deionized water and ammonia water into the solution, performing ultrasonic treatment on the mixed solution for 30-60 min, then dropwise adding tetraethyl orthosilicate (TEOS), and continuously stirring at room temperature for 4-5 h;
step four, obtaining SiO by centrifugal separation and discarding supernatant2Composite Ni-MOF (Ni-MOF @ SiO)2）；
Step five, taking Ni-MOF @ SiO2 Co composite 2,4, 6-tripyridyl triazine (CoTPTZ) and dicyanodiamine are fully and uniformly ground in a mortar;
and sixthly, placing the mixture obtained in the fifth step in a resistance furnace, performing constant-temperature carbonization treatment under the action of protective gas, naturally cooling to room temperature, performing acid washing and centrifugation on the collected sample to obtain a precipitate, and drying at the temperature of 85-90 ℃ to obtain Ni @ Co-MNC/CNTs.
Further, in the first step, the mass ratio of nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane is as follows: (3.2-3.5): (1.8-2): 1; the adding amount of DMF is 33-35 times of the molar amount of nickel chloride hexahydrate.
And further, the heating time of the oven in the second step is 48-60 h.
Further, in the third step, the concentration of the Ni-MOF in the absolute ethyl alcohol is 2-3 g/L; the mass ratio of the Ni-MOF to the hexadecyl trimethyl ammonium bromide is (1: 1) - (1: 1.5); the mass ratio of tetraethyl orthosilicate to Ni-MOF is (1: 4) - (1: 1); the volume ratio of the deionized water to the ammonia water to the mixed solution is (3: 1: 14) - (4: 1: 15).
Further, the room temperature in the third step is 24-28 ℃.
Further, the preparation method of the Co compounded 2,4, 6-tripyridyl triazine in the step five comprises the following steps: taking Co (NO)3) 2.6H 2O, 2,4, 6-tri (2-pyridyl) triazine (TPTZ), HCl solution and a proper amount of deionized water are stirred for 2-3H, and the mixture is dried by distillation at the temperature of 90-95 ℃ to obtain a sample CoTPTZ.
Further, Co (NO)3)2•6 H2O, TPTZ is (0.10-0.15) by mass: 1; the volume ratio of the HCl solution to the deionized water to the total mixed solution is 1: (4-5): (5-6).
Further, Ni-MOF @ SiO in step five2The mass ratio of CoTPTZ to dicyanodiamine is 1 (0.5-2) to (4-5).
Further, the protective gas in the sixth step is nitrogen or argon.
Further, the constant temperature carbonization conditions in the sixth step are as follows: the constant temperature is 800-900 ℃, and the heating rate is 5-10 ℃ for min-1And the heat preservation time is 120-150 min.
A Ni/Co-N doped porous carbon oxygen reduction catalyst prepared according to any one of claims 1 to 9.
The invention has the following beneficial effects that:
1) the invention uses SiO2The template is compounded in Ni-MOF in an in-situ embedding mode to remove SiO2Obtaining the material with a honeycomb structure after the microspheres. The method effectively constructs a three-dimensional porous carbon material skeleton and provides space and sites for in-situ growth of the carbon nano tube;
2) by adding the second metal Co into the reaction system, the second metal Co and the metal Ni are compounded to form a more efficient Ni/Co electrocatalytic active center, and the catalytic reaction capability of the material is further enhanced through the synergistic effect of the second metal Co and the metal Ni.
Drawings
FIG. 1 is an SEM image of a Ni @ Co-MNC/CNTs oxygen reduction catalyst prepared in example 1 of the present invention;
FIG. 2 is a TEM image of the Ni @ Co-MNC/CNTs oxygen reduction catalyst prepared in example 1 of the present invention;
FIG. 3 is a nitrogen adsorption and desorption curve of the Ni @ Co-MNC/CNTs catalyst prepared in example 1 of the present invention;
FIG. 4 is an LSV spectrum of the Ni @ Co-MNC/CNTs catalyst prepared in example 1 of the present invention in a 0.1M KOH electrolyte.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific examples, but the present invention is not limited thereto.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "lateral", "longitudinal", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
A preparation method of a Ni/Co-N doped porous carbon-oxygen reduction catalyst comprises the following steps:
step one, dissolving nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane in a N, N-dimethylformamide DMF solution;
placing the mixed solution into a reaction kettle, reacting in an oven with the reaction temperature of 120-130 ℃, cleaning the obtained green powder with a proper amount of DMF solution, and drying to obtain a Ni metal organic framework material (Ni-MOF);
dissolving Ni-MOF in absolute ethyl alcohol, performing ultrasonic treatment for 25-35 min, sequentially adding Cetyl Trimethyl Ammonium Bromide (CTAB), deionized water and ammonia water into the solution, performing ultrasonic treatment on the mixed solution for 30-60 min, then dropwise adding tetraethyl orthosilicate (TEOS), and continuously stirring at room temperature for 4-5 h;
step four, obtaining SiO by centrifugal separation and discarding supernatant2Composite Ni-MOF (Ni-MOF @ SiO)2）；
Step five, taking Ni-MOF @ SiO2 Co composite 2,4, 6-tripyridyl triazine (CoTPTZ) and dicyanodiamine are fully and uniformly ground in a mortar;
and sixthly, placing the mixture obtained in the fifth step in a resistance furnace, performing constant-temperature carbonization treatment under the action of protective gas, naturally cooling to room temperature, performing acid washing and centrifugation on the collected sample to obtain a precipitate, and drying at the temperature of 85-90 ℃ to obtain Ni @ Co-MNC/CNTs.
Further, in the first step, the mass ratio of nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane is as follows: (3.2-3.5): (1.8-2): 1; the adding amount of DMF is 33-35 times of the molar amount of nickel chloride hexahydrate.
And further, the heating time of the oven in the second step is 48-60 h.
Further, in the third step, the concentration of the Ni-MOF in the absolute ethyl alcohol is 2-3 g/L; the mass ratio of the Ni-MOF to the hexadecyl trimethyl ammonium bromide is (1: 1) - (1: 1.5); the mass ratio of tetraethyl orthosilicate to Ni-MOF is (1: 4) - (1: 1); the volume ratio of the deionized water to the ammonia water to the mixed solution is (3: 1: 14) - (4: 1: 15).
Further, the room temperature in the third step is 24-28 ℃.
Further, the preparation method of the Co-compounded 2,4, 6-tripyridyl triazine in the step five comprises the following steps: taking Co (NO)3) 2.6H 2O, 2,4, 6-tri (2-pyridyl) triazine (TPTZ), HCl solution and a proper amount of deionized water are stirred for 2-3H, and the mixture is dried by distillation at the temperature of 90-95 ℃ to obtain a sample CoTPTZ.
Further, Co (NO)3)2•6 H2O, TPTZ is (0.10-0.15) by mass: 1; the volume ratio of the HCl solution to the deionized water to the total mixed solution is 1: (4-5): (5-6).
Further, Ni-MOF @ SiO in step five2The mass ratio of CoTPTZ to dicyanodiamine is 1 (0.5-2) to (4-5).
Further, the protective gas in the sixth step is nitrogen or argon.
Further, the constant temperature carbonization conditions in the sixth step are as follows: the constant temperature is 800-900 ℃, and the heating rate is 5-10 ℃ for min-1And the heat preservation time is 120-150 min.
The catalyst is prepared by the method.
A Ni/Co-N doped porous carbon-oxygen reduction catalyst is prepared by the following steps:
step one, dissolving nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane in a N, N-dimethylformamide DMF solution; the mass ratio of nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane is as follows: 3.2: 1.8: 1; the adding amount of DMF is 33-35 times of the molar amount of nickel chloride hexahydrate;
placing the mixed solution into a reaction kettle, reacting in an oven with the reaction temperature of 120-130 ℃, heating the oven for 48-60 hours, repeatedly cleaning the obtained green powder with a proper amount of DMF (dimethyl formamide) solution for three times, and drying to obtain a Ni metal organic framework material (Ni-MOF);
dissolving Ni-MOF in absolute ethyl alcohol, performing ultrasonic treatment for 30min, sequentially adding Cetyl Trimethyl Ammonium Bromide (CTAB), deionized water and ammonia water with the volume fraction of 25-28% into the solution, performing ultrasonic treatment on the mixed solution for 30-60 min, dropwise adding tetraethyl orthosilicate (TEOS) into the mixed solution, and continuously stirring at room temperature for 4-5 h; the room temperature is 24-28 ℃; the mass ratio of the Ni-MOF to the hexadecyl trimethyl ammonium bromide is 1:1. the volume ratio of the deionized water to the ammonia water to the mixed solution is 3: 1: 14; the mass ratio of TEOS to Ni-MOF is 1: 4;
step four, obtaining SiO by centrifugal separation and discarding supernatant2Composite Ni-MOF (Ni-MOF @ SiO)2）；
Step five, taking Ni-MOF @ SiO2Co composite 2,4, 6-tripyridyl triazine (CoTPTZ) and dicyanodiamine are fully and uniformly ground in a mortar; Ni-MOF @ SiO2The mass ratio of CoTPTZ to dicyanodiamine is 1:1: 5;
sixthly, placing the mixture obtained in the fifth step in a resistance furnace, performing constant-temperature carbonization treatment under the action of protective gas, wherein the protective gas is nitrogen or argon, naturally cooling to room temperature, and washing the collected sample with HF (hydrogen fluoride) with the volume fraction of 10% for 6 hours to remove SiO2The precipitate collected by centrifugation is dried in an oven at 85 ℃ to obtain Ni @ CoX-MNC/CNTs (X is the ratio between Ni and Co additions); the constant temperature carbonization conditions are as follows: the constant temperature is 800 ℃, and the heating rate is 5°C min-1The heat preservation time is 120 min.
The preparation method of the Co composite 2,4, 6-tripyridyl triazine in the step five comprises the following steps: taking Co (NO)3)2•6 H2And (3) adding O, 2,4, 6-tri (2-pyridyl) triazine (TPTZ), HCl solution and a proper amount of deionized water, stirring for 2-3 h, and evaporating the mixture to remove water at the temperature of 90-95 ℃ to obtain a sample CoTPTZ. Co (NO)3)2•6 H2O, TPTZ is (0.10-0.15) by mass: 1; the volume ratio of the HCl solution to the deionized water to the total mixed solution is 1: (4-5): (5-6).
The Ni/Co-N doped porous carbon-oxygen reduction catalyst prepared according to the scheme has good oxygen reduction catalytic capability. The invention adopts a hydrothermal method to prepare Ni-MOF as a matrix material, and SiO is introduced into a system2The ball is used as a template and the carbon nano tube grows in situ, and the three-dimensional porous carbon structure is successfully constructed. And on the basis of the growth of the three-dimensional porous carbon and the carbon nano tube, a second metal Co element is continuously added into the material to form a Ni/Co high-efficiency catalytic center so as to further improve the catalytic activity of the material.
Example 1
A Ni @ Co-MNC/CNTs oxygen reduction catalyst is prepared by the following steps:
1) 0.107 g of nickel chloride hexahydrate, 0.060 g of 1, 4-terephthalic acid and 0.033 g of 1, 4-diazabicyclo [2.2.2] octane were dissolved in 15 mL of a N, N-Dimethylformamide (DMF) solution.
2) And (3) placing the mixed solution in a reaction kettle, and placing the mixture in a 120 ℃ oven for reaction for 48 hours. And repeatedly washing the obtained green powder with an appropriate amount of DMF solution for three times, and drying for later use.
3) Dissolving 0.2 g of Ni-MOF in 100 mL of absolute ethanol, and carrying out ultrasonic treatment for 30 min. 0.2 g of hexadecyl trimethyl ammonium bromide (CTAB), 30 mL of deionized water and 10 mL of ammonia water solution with the volume fraction of 25-28% are sequentially added into the solution, the mixed solution is subjected to ultrasonic treatment for 30min, then 0.8 g of tetraethyl orthosilicate (TEOS) solution is dropwise added, and the stirring is kept for 4 h.
4) And centrifuging, and removing the supernatant to obtain a sample, namely Ni-MOF @ SiO 2.
5) 0.2 g of Ni-MOF @ SiO2, 0.2 g of CoTPTZ and 1.0 g of dicyanodiamide were thoroughly and homogeneously ground in a mortar.
6) And (2) placing the mixture in a tubular resistance furnace, raising the temperature to 800 ℃ at the temperature of 5 ℃ for min-1 under the protection of high-purity nitrogen, preserving the heat for 2 h, naturally cooling to room temperature, washing the collected sample with HF with the volume fraction of 10% for 6 h to remove SiO2, and placing the precipitate collected by centrifugation in an oven at the temperature of 85 ℃ for drying to obtain the Ni @ Co-MNC/CNTs.
SEM and TEM electron scans are carried out on the product Ni @ Co-MNC/CNTs prepared in the embodiment, nitrogen adsorption and desorption tests are carried out on the product Ni @ Co-MNC/CNTs, the Ni @ Co-MNC/CNTs oxygen reduction catalyst prepared in the embodiment is electrochemically tested in 0.1M KOH electrolyte, and an SEM image, a TEM image, a nitrogen adsorption and desorption curve and an LSV image of the product are respectively shown in figures 1, 2, 3 and 4; the results show that: as can be seen from fig. 1, the prepared material has a carbon nanotube structure; FIG. 2 further demonstrates the hollow structure of the carbon nanotubes in the material; FIG. 3 shows a typical type-IV adsorption isotherm, indicating its porous structure, and the inset shows that the pore size distribution of the material is concentrated around 3.8 nm; the results in FIG. 4 show that the Ni @ Co-MNC/CNTs catalyst exhibits the best catalytic activity and the highest peak potential (around 0.947V vs. RHE).
Example 2
A Ni @ Co0.5-MNC/CNTs oxygen reduction catalyst is prepared by the following steps:
1) 0.107 g of nickel chloride hexahydrate, 0.060 g of 1, 4-terephthalic acid and 0.033 g of 1, 4-diazabicyclo [2.2.2] octane were dissolved in 15 mL of a N, N-Dimethylformamide (DMF) solution.
2) And (3) placing the mixed solution in a reaction kettle, and placing the mixture in a 120 ℃ oven for reaction for 48 hours. And repeatedly washing the obtained green powder with an appropriate amount of DMF solution for three times, and drying for later use.
3) Dissolving 0.2 g of Ni-MOF in 100 mL of absolute ethanol, and carrying out ultrasonic treatment for 30 min. 0.2 g of hexadecyl trimethyl ammonium bromide (CTAB), 30 mL of deionized water and 10 mL of ammonia water solution with the volume fraction of 25-28% are sequentially added into the solution, the mixed solution is subjected to ultrasonic treatment for 30min, then 0.8 g of tetraethyl orthosilicate (TEOS) solution is dropwise added, and the stirring is kept for 4 h.
4) And centrifuging, and removing the supernatant to obtain a sample, namely Ni-MOF @ SiO 2.
5) 0.2 g of Ni-MOF @ SiO2, 0.1 g of CoTPTZ and 1.0 g of dicyanodiamide were thoroughly and homogeneously ground in a mortar.
6) And (2) placing the mixture in a tubular resistance furnace, raising the temperature to 800 ℃ at the temperature of 5 ℃ min-1 under the protection of high-purity nitrogen, preserving the heat for 2 hours, naturally cooling to room temperature, washing the collected sample with 10% by volume of HF for 6 hours to remove SiO2, and placing the precipitate collected by centrifugation in an oven at the temperature of 85 ℃ for drying to obtain the Ni @ Co0.5-MNC/CNTs.
The Ni @ Co0.5-MNC/CNTs oxygen reduction catalyst prepared in the embodiment is subjected to electrochemical test in 0.1M KOH electrolyte, and the oxygen reduction peak potential is about 0.909V vs.
Example 3
A Ni @ Co1.5-MNC/CNTs oxygen reduction catalyst is prepared by the following steps:
1) 0.107 g of nickel chloride hexahydrate, 0.060 g of 1, 4-terephthalic acid and 0.033 g of 1, 4-diazabicyclo [2.2.2] octane were dissolved in 15 mL of a N, N-Dimethylformamide (DMF) solution.
2) And (3) placing the mixed solution in a reaction kettle, and placing the mixture in a 120 ℃ oven for reaction for 48 hours. And repeatedly washing the obtained green powder with an appropriate amount of DMF solution for three times, and drying for later use.
3) Dissolving 0.2 g of Ni-MOF in 100 mL of absolute ethanol, and carrying out ultrasonic treatment for 30 min. 0.2 g of hexadecyl trimethyl ammonium bromide (CTAB), 30 mL of deionized water and 10 mL of ammonia water solution with the volume fraction of 25-28% are sequentially added into the solution, the mixed solution is subjected to ultrasonic treatment for 30min, then 0.8 g of tetraethyl orthosilicate (TEOS) solution is dropwise added, and the stirring is kept for 4 h.
4) And centrifuging, and removing the supernatant to obtain a sample, namely Ni-MOF @ SiO 2.
5) 0.2 g of Ni-MOF @ SiO2, 0.3 g of CoTPTZ and 1.0 g of dicyanodiamide were thoroughly and homogeneously ground in a mortar.
6) And (2) placing the mixture in a tubular resistance furnace, raising the temperature to 800 ℃ at the temperature of 5 ℃ min-1 under the protection of high-purity nitrogen, preserving the heat for 2 hours, naturally cooling to room temperature, washing the collected sample with 10% by volume of HF for 6 hours to remove SiO2, and placing the precipitate collected by centrifugation in an oven at the temperature of 85 ℃ for drying to obtain the Ni @ Co1.5-MNC/CNTs.
The Ni @ Co1.5-MNC/CNTs oxygen reduction catalyst prepared in the embodiment is subjected to electrochemical test in 0.1M KOH electrolyte, and the oxygen reduction peak potential is about 0.851V vs.
Example 4
A Ni @ Co2-MNC/CNTs oxygen reduction catalyst is prepared by the following steps:
1) 0.107 g of nickel chloride hexahydrate, 0.060 g of 1, 4-terephthalic acid and 0.033 g of 1, 4-diazabicyclo [2.2.2] octane were dissolved in 15 mL of a N, N-Dimethylformamide (DMF) solution.
2) And (3) placing the mixed solution in a reaction kettle, and placing the mixture in a 120 ℃ oven for reaction for 48 hours. And repeatedly washing the obtained green powder with an appropriate amount of DMF solution for three times, and drying for later use.
3) Dissolving 0.2 g of Ni-MOF in 100 mL of absolute ethanol, and carrying out ultrasonic treatment for 30 min. 0.2 g of hexadecyl trimethyl ammonium bromide (CTAB), 30 mL of deionized water and 10 mL of ammonia water solution with the volume fraction of 25-28% are sequentially added into the solution, the mixed solution is subjected to ultrasonic treatment for 30min, then 0.8 g of tetraethyl orthosilicate (TEOS) solution is dropwise added, and the stirring is kept for 4 h.
4) And centrifuging, and removing the supernatant to obtain a sample, namely Ni-MOF @ SiO 2.
5) 0.2 g of Ni-MOF @ SiO2, 0.4 g of CoTPTZ and 1.0 g of dicyanodiamide were thoroughly and homogeneously ground in a mortar.
6) And (2) placing the mixture in a tubular resistance furnace, raising the temperature to 800 ℃ at the temperature of 5 ℃ for min-1 under the protection of high-purity nitrogen, preserving the heat for 2 hours, naturally cooling to room temperature, washing the collected sample with HF with the volume fraction of 10% for 6 hours to remove SiO2, and placing the precipitate collected by centrifugation in an oven at the temperature of 85 ℃ for drying to obtain Ni @ Co 2-MNC/CNTs.
The Ni @ Co2-MNC/CNTs oxygen reduction catalyst prepared in the embodiment is subjected to electrochemical test in 0.1M KOH electrolyte, and the oxygen reduction peak potential is about 0.848V vs.
The above examples are not specifically described, and the reagents used in the present invention are commercially available as chemical reagents or industrial products, the present invention can be realized by the ratios of the raw materials listed in the present invention, the values of the upper and lower limits and the intervals of the raw materials can be realized by the values of the upper and lower limits of the process parameters of the present invention, and the present invention can be realized by the values of the upper and lower limits and the intervals of the process parameters of the present invention, but the examples are not specifically listed here.
In addition to the above embodiments, the present invention may have other forms, and it should be noted that any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (10)
1. A preparation method of a Ni/Co-N doped porous carbon-oxygen reduction catalyst is characterized by comprising the following steps: the method comprises the following steps:
step one, dissolving nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane in a N, N-dimethylformamide DMF solution;
placing the mixed solution into a reaction kettle, reacting in an oven with the reaction temperature of 120-130 ℃, cleaning the obtained green powder with a proper amount of DMF solution, and drying to obtain a Ni metal organic framework material (Ni-MOF);
dissolving Ni-MOF in absolute ethyl alcohol, performing ultrasonic treatment for 25-35 min, sequentially adding Cetyl Trimethyl Ammonium Bromide (CTAB), deionized water and ammonia water into the solution, performing ultrasonic treatment on the mixed solution for 30-60 min, then dropwise adding tetraethyl orthosilicate (TEOS), and continuously stirring at room temperature for 4-5 h;
step four, obtaining SiO by centrifugal separation and discarding supernatant2Composite Ni-MOF (Ni-MOF @ SiO)2）；
Step five, taking Ni-MOF @ SiO2Co composite 2,4, 6-tripyridyl triazine (CoTPTZ) and dicyanodiamine are fully and uniformly ground in a mortar;
and sixthly, placing the mixture obtained in the fifth step in a resistance furnace, performing constant-temperature carbonization treatment under the action of protective gas, naturally cooling to room temperature, performing acid washing and centrifugation on the collected sample to obtain a precipitate, and drying at the temperature of 85-90 ℃ to obtain Ni @ Co-MNC/CNTs.
2. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: in the first step, the mass ratio of nickel chloride hexahydrate, 1, 4-terephthalic acid and 1, 4-diazabicyclo [2.2.2] octane is as follows: (3.2-3.5): (1.8-2): 1; the adding amount of DMF is 33-35 times of the molar amount of nickel chloride hexahydrate.
3. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: and in the second step, the heating time of the oven is 48-60 h.
4. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: in the third step, the concentration of the Ni-MOF in the absolute ethyl alcohol is 2-3 g/L; the mass ratio of the Ni-MOF to the hexadecyl trimethyl ammonium bromide is (1: 1) - (1: 1.5); the mass ratio of tetraethyl orthosilicate to Ni-MOF is (1: 4) - (1: 1); the volume ratio of the deionized water to the ammonia water to the mixed solution is (3: 1: 14) - (4: 1: 15).
5. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: the room temperature in the third step is 24-28 ℃.
6. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: the preparation method of the Co composite 2,4, 6-tripyridyl triazine in the step five comprises the following steps: taking Co (NO)3) 2.6H 2O, 2,4, 6-tri (2-pyridyl) triazine (TPTZ), HCl solution and a proper amount of deionized water are stirred for 2-3 hours, and the mixture is dried by distillation at the temperature of 90-95 ℃ to obtain a sample CoTPTZ;wherein, Co (NO)3)2•6 H2O, TPTZ is (0.10-0.15) by mass: 1; the volume ratio of the HCl solution to the deionized water to the total mixed solution is 1: (4-5): (5-6).
7. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: Ni-MOF @ SiO in step five2The mass ratio of CoTPTZ to dicyanodiamine is 1 (0.5-2) to (4-5).
8. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: and the protective gas in the sixth step is nitrogen or argon.
9. The method for preparing the Ni/Co-N doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: and step six, the constant temperature carbonization conditions are as follows: the constant temperature is 800-900 ℃, and the heating rate is 5-10 ℃ for min-1And the heat preservation time is 120-150 min.
10. A Ni/Co-N doped porous carbon-oxygen reduction catalyst is characterized in that: the catalyst is prepared by any one of claims 1 to 9.
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| CN114657592A (en) * | 2022-04-25 | 2022-06-24 | 南昌航空大学 | Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof |
| CN114744162A (en) * | 2022-06-09 | 2022-07-12 | 中博龙辉装备集团股份有限公司 | Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
| CN115724420A (en) * | 2022-09-30 | 2023-03-03 | 重庆长安新能源汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application, coated positive electrode material and preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114657592A (en) * | 2022-04-25 | 2022-06-24 | 南昌航空大学 | Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof |
| CN114657592B (en) * | 2022-04-25 | 2023-08-08 | 南昌航空大学 | Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
| CN114768878B (en) * | 2022-05-07 | 2024-05-10 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
| CN114744162A (en) * | 2022-06-09 | 2022-07-12 | 中博龙辉装备集团股份有限公司 | Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof |
| CN115724420A (en) * | 2022-09-30 | 2023-03-03 | 重庆长安新能源汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application, coated positive electrode material and preparation method |
| CN115724420B (en) * | 2022-09-30 | 2024-04-16 | 深蓝汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application and coated anode material and preparation method thereof |
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