CN114277399A - Ni monatomic-nitrogen-doped carbon nano-catalyst, preparation method thereof and flue gas conversion application - Google Patents
Ni monatomic-nitrogen-doped carbon nano-catalyst, preparation method thereof and flue gas conversion application Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon nano-catalyst doped with Ni single atoms, and a preparation method and application thereof. The nitrogen-doped carbon nano catalyst doped with Ni single atoms comprises a carbon material and Ni atoms which are mutually independent and loaded on the surface of the carbon. The invention constructs the nitrogen-doped carbon nano catalyst doped with the Ni monoatomic atom by loading the Ni monoatomic atom on the nitrogen-doped carbon substrate in an isolated way, not only overcomes the problems of complex preparation process and high cost of scale production of the monoatomic catalyst, but also enables the obtained nitrogen-doped carbon nano catalyst doped with the Ni monoatomic atom to have high catalytic activity and selectivity in preparing carbon monoxide by catalyzing flue gas electroreduction reaction based on the high-efficiency atom utilization rate of the monoatomic atom and strong interaction of the metal substrate, and also keeps high activity and selectivity in low-concentration carbon dioxide feed gas simulating flue gas components, thereby being expected to be applied to high-efficiency conversion of carbon dioxide gas in flue gas.
Description
Technical Field
The invention relates to the technical field of energy catalysis, in particular to a Ni monatomic-nitrogen-doped carbon nano-catalyst and a preparation method and application thereof.
Background
In recent years, along with the increasing problems of environmental pollution, energy crisis and the like, the technology for preparing carbon related products by electrocatalysis carbon dioxide reduction is widely concerned, which is part of the content that the carbon dioxide emission strives to reach the peak value before 2030 years and strives to realize the carbon neutralization target before 2060 years in China. Carbon monoxide is used as a main component of basic chemical raw materials such as synthesis gas and the like, and has wide application prospects in the fields of chemical industry and medicines. Although the technology for preparing carbon monoxide by electrochemical reduction of carbon dioxide is relatively mature, many problems of poor selection of a catalyst, large-scale production cost, high and low selectivity of a product, low solubility of carbon dioxide and the like still need to be solved.
Flue gas is a gaseous substance which is produced by burning fossil fuels such as coal and pollutes the environment. As these materials are typically exhausted from a flue or stack. The flue gas generation process is mostly caused by incomplete combustion due to insufficient utilization of fuel, and the components of the flue gas include nitrogen, carbon dioxide, oxygen, water vapor, sulfide and the like. Flue gases from coal-fired power plants are one of the main sources of carbon emissions, where the composition of carbon dioxide is related to the fuel properties (type, composition, state, etc.) and the process: 15-25% of industrial furnace, 10-15% of coal-fired boiler, 85-90% of integrated gasification combined cycle combustion technology, 6-10% of oil-fired boiler and more than 5-8% of gas-fired boiler. In view of the high cost of carbon capture, the efficient conversion of carbon dioxide in flue gas by electrocatalytic reduction directly from flue gas is also a significant challenge, with the promise of being an important approach to flue gas utilization. At present, the carbon monoxide prepared by direct electroreduction of flue gas mainly faces the problem of maintaining the electroreduction activity and selectivity of carbon dioxide under low concentration.
In terms of catalyst selection, the traditional noble metal catalyst has good activity, but is expensive and is easy to be poisoned by sulfur. A small amount of metal monoatomic atoms are loaded on a solid substrate by the emerging monoatomic catalyst, the reaction activation energy is reduced through the strong interaction between the metal monoatomic active centers and the substrate, the catalyst has obvious activity in the reactions, the utilization efficiency of catalytic sites can be effectively improved, and the cost is reduced. Nickel metal monoatomic species, which are abundant in the earth, have been shown to have a high selectivity for carbon monoxide. However, the problems of complicated preparation technology of the monatomic catalyst, difficult large-scale production, difficult synthesis of the carbon precursor and the like still restrict the technology of using the monatomic catalyst to electrically reduce the carbon dioxide.
Disclosure of Invention
Technical problem to be solved
The problem that the technology of using the monatomic catalyst to electroreduce carbon dioxide is still restricted by the problems that the monatomic catalyst preparation technology is complex, large-scale production is not easy, carbon precursor synthesis is difficult and the like is solved, and the Ni monatomic-nitrogen doped carbon nanocatalyst and the preparation method and the application thereof are provided.
(II) technical scheme
A Ni single atom-nitrogen doped carbon nano catalyst comprises nitrogen doped carbon and Ni atoms which are mutually independently loaded on the surface of a carbon material.
As a preferred embodiment, the nitrogen-doped carbon includes, but is not limited to, nitrogen-doped activated carbon black, nitrogen-doped graphite powder, nitrogen-doped graphene, nitrogen-doped carbon nanotubes, and the like.
As a preferred technical scheme, the mass ratio of Ni atoms to nitrogen-doped carbon is 3-4: 95 to 105.
As a preferable technical scheme, the catalyst is applied to the reaction of preparing carbon monoxide by electrocatalytic conversion of flue gas.
A preparation method of a Ni monatomic-nitrogen-doped carbon nano-catalyst comprises the following steps: dispersing the activated carbon material in deionized water to obtain a mixed solution A; adding a nickel nitrate solution into the mixed solution A to obtain a mixed solution B; centrifugally collecting the mixed solution B, washing and drying the obtained reaction product to obtain Ni2+-a carbon powder; ni to be prepared2+Carbon powder mixed with urea for high temperature sintering, or Ni prepared2+-carbon powder in NH3Calcining at high temperature in the atmosphere of 75-85 sccm ammonia gas or argon gas at the sintering temperature of 750-850 ℃ for 0.5-1.5 h to obtain the Ni monatomic-nitrogen-doped carbon nano catalyst, wherein the Ni is2+-the mass ratio of carbon powder to urea is 95-105 (mg): 0.9 to 1.1 (g).
As a preferred technical scheme, the mass-to-volume ratio of the activated carbon material to deionized water is 95-105 (mg): 30-40 (mL), and the concentration of the nickel nitrate solution is 2.8-3.2 mg/mL.
According to the preferable technical scheme, the adding speed of the nickel nitrate solution is 19-21 mL/h, the stirring reaction time of the mixed solution B is 6-8 h, and the rotating speed of the stirrer is 1000-1200 r/min.
As a preferred technical scheme, the washing treatment adopts a polar solvent, and the specific operation process of the washing treatment is as follows: and carrying out centrifugal separation on the mixed solution B after reaction, carrying out ultrasonic washing on a product obtained by the centrifugal separation by using a polar solvent, then continuing carrying out the centrifugal separation, and carrying out ultrasonic washing on the product obtained by the centrifugal separation by using the polar solvent, wherein the ultrasonic washing time is 1-2 min each time, the rotating speed of the centrifugal separation is 7000-8000 r/min each time, and the time of the centrifugal separation is 5-7 min each time.
As a preferred technical scheme, the high-temperature sintering treatment specifically comprises the following operations: and putting the mixed sample into a crucible, placing the crucible into a tube furnace for sintering, cooling to room temperature, and collecting the sintered product.
As a preferred embodiment, the method for activating the carbon material is as follows: dispersing a carbon material in nitric acid for dissolving, then carrying out condensation reflux on the activated carbon material, then cooling to room temperature, washing and drying the obtained product to obtain the activated carbon material, wherein the mass-volume ratio of the carbon material to 9M nitric acid solution is 1.8-2.2 (g): 100(mL), the temperature of condensation reflux is 85-95 ℃, and the time of condensation reflux is 2-4 h.
(III) advantageous effects
The invention has the beneficial effects that:
(1) the Ni monatomic-nitrogen doped carbon nano-catalyst is loaded on the carbon material substrate in an isolated manner, so that the Ni monatomic-nitrogen doped carbon nano-catalyst is constructed, the high-efficiency carbon monoxide selectivity is realized, and the problems of economic requirements of carbon precursors and monatomic catalysts and easiness in preparation and expansion can be solved due to the wide use of carbon materials including active carbon black, graphite, graphene, carbon nano-tubes and the like.
(2) The preparation method of the Ni monatomic-nitrogen-doped carbon nano-catalyst can obtain the monatomic catalyst with high load and mutually independent Ni atoms. The method has the advantages of few special equipment required by experiments, easiness in preparation, excellent selectivity and activity in the reaction of catalyzing CO2 to prepare CO through electro-reduction, high activity and selectivity on CO even when low-concentration (20 percent and 2 percent) CO2 simulating flue gas components is used as raw material gas, and suitability for high-efficiency conversion of CO2 in the flue gas.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray energy spectrum of the Ni monatomic-nitrogen-doped activated carbon nano-catalyst obtained in example 1 of the present invention;
FIG. 2 is a scanning transmission electron microscope high-angle annular dark field image of the Ni monatomic-nitrogen-doped activated carbon nano-catalyst obtained in example 1 of the present invention;
FIG. 3 is a schematic view of a membrane electrode assembly reactor for evaluating the performance of the carbon dioxide electroreduction reaction according to example 5 of the present invention;
fig. 4 shows the faradaic efficiency of each product at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes carbon dioxide electroreduction reaction, and 100% pure carbon dioxide is used as a raw material gas;
fig. 5 shows the total current and the carbon monoxide bias current density at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes the carbon dioxide electroreduction reaction, and 100% pure carbon dioxide is used as a raw material gas;
fig. 6 shows the faradaic efficiency of each product at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes carbon dioxide electroreduction reaction, and 20% pure carbon dioxide is used as a raw material gas;
fig. 7 shows the carbon monoxide bias current densities at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes carbon dioxide electroreduction reaction, and 20% pure carbon dioxide is used as a raw material gas;
fig. 8 shows the faradaic efficiency of each product at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes carbon dioxide electroreduction reaction, and 2% pure carbon dioxide is used as a raw material gas;
fig. 9 shows the carbon monoxide bias current densities at different potentials when the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention catalyzes carbon dioxide electroreduction reaction, and 2% pure carbon dioxide is used as a raw material gas.
Detailed Description
The Ni monatomic-nitrogen-doped carbon nanocatalyst, the preparation method thereof and the flue gas conversion application of the present invention will be further described with reference to the accompanying drawings, and the present invention will be further detailed with reference to the following examples:
example 1:
preparation of Ni monatomic-nitrogen doped active carbon nano-catalyst
(1) Dissolving commercial carbon black into nitric acid under normal temperature stirring, wherein the mass of the carbon black is 2.15g, the concentration of the nitric acid is 8mol/L, the volume is 100mL, the carbon black is uniformly dispersed in the nitric acid solution after ultrasonic treatment for 5min, the mixed solution is placed in a flask for condensation reflux, the reflux temperature is 85 ℃, the reaction time is 4h, then the mixed solution is cooled to room temperature, the solid material cooled to the room temperature is subjected to centrifugal separation, the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 6min, the product obtained by the centrifugal separation is subjected to ultrasonic washing for 3min by using a polar solvent, then the centrifugal separation is continued, the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 7min, the product obtained by the centrifugal separation is subjected to ultrasonic washing for 2min by using the polar solvent, and vacuum drying is carried out at 65 ℃ overnight to obtain active carbon black;
(2) uniformly dispersing active carbon black in a deionized water solution to obtain a mixed solution A, wherein the mass of the carbon black is 980mg, and the volume of the deionized water is 420 mL; adding a nickel nitrate solution into the mixed solution A under stirring at room temperature, and violently stirring to obtain a mixed solution B; the concentration of the nickel nitrate solution is 3.0mg/mL, the volume of the nickel nitrate solution is 42mL, and the adding speed is about 20mL/h by using a manual slow dropping mode. Continuing to stir the mixed solution B at room temperature for 7 hours, performing centrifugal separation on the stirred material at the rotating speed of 7600 r/min for 7 minutes, performing ultrasonic washing on the product obtained by centrifugation for 1min by using a polar solvent, continuing to perform centrifugal separation at the rotating speed of 7600 r/min for 5min, performing ultrasonic washing on the product obtained by centrifugation for 2min by using the polar solvent, and performing vacuum drying to obtain Ni2+Carbon black powder of Ni2+-carbon black powder and urea in a volume ratio of 1: 9.5, uniformly mixing, placing the mixed sample in a crucible, placing the crucible in a tubular furnace, and sintering at high temperature for 0.9h, wherein the sintering atmosphere is 80sccm argon, the sintering temperature is 280 ℃, and the reaction time of sintering is 0.9h, thus obtaining the Ni monatomic-nitrogen doped active carbon nano catalyst.
Through detection, the mass fraction of Ni atoms in the Ni monatomic-nitrogen-doped active carbon nano-catalyst obtained in the embodiment is 0.4 wt%.
Example 2:
preparation of Ni monatomic-nitrogen doped graphite nano-catalyst
(1) Dissolving graphite powder into nitric acid under stirring at normal temperature, wherein the mass of the graphite powder is 1.95g, the concentration of the nitric acid is 9mol/L, the volume of the nitric acid is 120mL, carrying out ultrasonic treatment for 3min to uniformly disperse the graphite powder in a nitric acid solution, placing a mixed solution into a flask for condensation reflux, wherein the reflux temperature is 85 ℃, the reaction time is 2.5h, then cooling to room temperature, carrying out centrifugal separation on a solid material cooled to the room temperature, the rotating speed of the centrifugal separation is 7400 r/min, the time of the centrifugal separation is 3min, carrying out ultrasonic washing on a product obtained by the centrifugal separation for 3min by using a polar solvent, then continuing the centrifugal separation, the rotating speed of the centrifugal separation is 7400 r/min, the time of the centrifugal separation is 5min, carrying out ultrasonic washing on the product obtained by the centrifugal separation for 2min by using the polar solvent, and carrying out vacuum drying at 65 ℃ overnight to obtain active graphite powder;
(2) uniformly dispersing active graphite powder in a deionized water solution to obtain a mixed solution A, wherein the mass of the active graphite powder is 990mg, and the volume of the deionized water is 410 mL; adding a nickel nitrate solution into the mixed solution A under stirring at room temperature, and violently stirring to obtain a mixed solution B; the concentration of the nickel nitrate solution is 3.0mg/mL, the volume of the nickel nitrate solution is 41mL, and the adding speed is about 15mL/h by using a manual slow dropping mode. Continuing to stir the mixed solution B at room temperature for 7.5 hours, performing centrifugal separation on the stirred material, wherein the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 6 minutes, performing ultrasonic washing on the product obtained by the centrifugal separation for 2 minutes by using a polar solvent, then continuing to perform the centrifugal separation, wherein the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 5 minutes, performing ultrasonic washing on the product obtained by the centrifugal separation for 2 minutes by using the polar solvent, and performing vacuum drying to obtain Ni2+Graphite powder, adding Ni2+-graphite powder and urea in a volume ratio of 1: 8.5, uniformly mixing, placing the mixed sample in a crucible, placing the crucible in a tubular furnace, and sintering at the high temperature of argon gas of 80sccm, wherein the sintering temperature is 290 ℃, and the sintering reaction time is 1.2h, thus obtaining the Ni monatomic-nitrogen doped graphite nano catalyst.
Through detection, the mass fraction of Ni atoms in the Ni monatomic-nitrogen-doped graphite nano-catalyst obtained in the embodiment is 0.2 wt%.
Example 3:
preparation of Ni monatomic-nitrogen doped graphene nano-catalyst
(1) Dissolving graphene into nitric acid under normal-temperature stirring, wherein the mass of the graphene is 1.98g, the concentration of the nitric acid is 9mol/L, the volume of the nitric acid is 115mL, carrying out ultrasonic treatment for 3min to uniformly disperse the graphene in a nitric acid solution, placing a mixed solution into a flask for condensation reflux, wherein the reflux temperature is 87 ℃, the reaction time is 2.3h, then cooling to room temperature, carrying out centrifugal separation on a solid material cooled to the room temperature, wherein the rotating speed of the centrifugal separation is 7700 r/min, the time of the centrifugal separation is 3min, carrying out ultrasonic washing on a product obtained by the centrifugal separation for 3min by using a polar solvent, then continuing carrying out the centrifugal separation, wherein the rotating speed of the centrifugal separation is 7700 r/min, the time of the centrifugal separation is 5min, carrying out ultrasonic washing on the product obtained by using the polar solvent for 2min, and carrying out vacuum drying at 63 ℃ overnight to obtain active graphene;
(2) uniformly dispersing active graphene in a deionized water solution to obtain a mixed solution A, wherein the mass of the active graphene is 970mg, and the volume of the deionized water is 410 mL; adding a nickel nitrate solution into the mixed solution A under stirring at room temperature, and violently stirring to obtain a mixed solution B; the concentration of the nickel nitrate solution is 4.0mg/mL, the volume of the nickel nitrate solution is 41mL, and the adding speed is about 15mL/h by using a manual slow dropping mode. Continuing to stir the mixed solution B at room temperature for 7.5 hours, performing centrifugal separation on the stirred material, wherein the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 6 minutes, performing ultrasonic washing on the product obtained by the centrifugal separation for 2 minutes by using a polar solvent, then continuing to perform the centrifugal separation, wherein the rotating speed of the centrifugal separation is 8000 revolutions per minute, the time of the centrifugal separation is 5 minutes, performing ultrasonic washing on the product obtained by the centrifugal separation for 2 minutes by using the polar solvent, and performing vacuum drying to obtain Ni2+Graphene, coupling Ni2+-graphene and urea in a volume ratio of 1: 7, uniformly mixing, placing the mixed sample in a crucible, placing the crucible in a tubular furnace, and sintering at the high temperature for 1.5 hours under the atmosphere of 90sccm argon at the sintering temperature of 300 ℃ to obtain the Ni monatomic-nitrogen doped graphene nano catalyst.
Through detection, the mass fraction of the Ni atoms in the Ni monatomic-nitrogen-doped graphene nano-catalyst obtained in the embodiment is 0.5 wt%.
Example 4:
preparation of Ni monatomic-nitrogen-doped carbon nanotube nano-catalyst
(1) Dissolving carbon nanotubes into nitric acid under stirring at normal temperature, wherein the mass of the carbon nanotubes is 2.02g, the concentration of the nitric acid is 9mol/L, the volume of the nitric acid is 110mL, ultrasonic treatment is carried out for 10min to uniformly disperse the carbon nanotubes in a nitric acid solution, the mixed solution is placed in a flask for condensation reflux, the reflux temperature is 87 ℃, the reaction time is 2.3h, then cooling to room temperature, carrying out centrifugal separation on the solid material cooled to room temperature, wherein the rotating speed of the centrifugal separation is 7900 r/min, the time of the centrifugal separation is 5min, carrying out ultrasonic washing on the product obtained by the centrifugal separation for 5min by using a polar solvent, then continuing to carry out centrifugal separation at the rotating speed of 7900 r/min for 5min, carrying out ultrasonic washing on the product obtained by centrifugal separation for 2min by using a polar solvent, and carrying out vacuum drying at 60 ℃ overnight to obtain an activated carbon nanotube;
(2) uniformly dispersing the activated carbon nanotubes in a deionized water solution to obtain a mixed solution A, wherein the mass of the activated carbon nanotubes is 965mg, and the volume of the deionized water is 410 mL; adding a nickel nitrate solution into the mixed solution A under stirring at room temperature, and violently stirring to obtain a mixed solution B; the concentration of the nickel nitrate solution is 2.5mg/mL, the volume of the nickel nitrate solution is 45mL, and the adding speed is about 25mL/h by using a manual slow dropping mode. Continuing to stir the mixed solution B at room temperature for 8.5 hours, performing centrifugal separation on the stirred material at the rotating speed of 7500 r/min for 6 minutes, performing ultrasonic washing on the product obtained by centrifugation for 2 minutes by using a polar solvent, continuing to perform centrifugal separation at the rotating speed of 7500 r/min for 5 minutes, performing ultrasonic washing on the product obtained by centrifugation for 2 minutes by using the polar solvent, and performing vacuum drying to obtain Ni2 +Carbon nanotubes of Ni2+-carbon nanotubes to urea in a volume ratio of 1: 8, uniformly mixing, placing the mixed sample in a crucible, placing the crucible in a tubular furnace, and sintering at high temperature, wherein the sintering atmosphere is 85sccm argon, the sintering temperature is 320 ℃, and the sintering reaction time is 1h, so as to obtain the Ni monatomic-nitrogen-doped carbon nanotube nano-catalyst.
Through detection, the mass fraction of the Ni atom in the Ni monatomic-nitrogen-doped carbon nanotube nano-catalyst obtained in the present example was 0.2 wt%.
Example 5:
CO2 electroreduction catalytic performance test of Ni monatomic-nitrogen-doped activated carbon nano catalyst by taking CO2 pure gas as raw material
Referring to fig. 3, a carbon gas diffusion layer 1 loaded with the Ni monatomic-nitrogen-doped activated carbon nanocatalyst obtained in example 1 of the present invention is used as a cathode, and an anion exchange membrane 2 is tightly attached to the surface of the catalyst in a membrane electrode assembly reactor; iridium oxide loaded by carbon paper is taken as an anode and is tightly attached to the other side of the anion exchange membrane. Silica gel gaskets 3 are added on two sides to ensure the sealing performance, titanium plates are added to serve as current collectors, carbon dioxide electroreduction performance test is carried out in a membrane electrode assembly by taking CO2 pure gas as raw material gas, the flow rate of carbon dioxide 4 is kept at 50sccm in the test process, and the flow rate of anode potassium hydroxide electrolyte 5 is kept at 60 mL/h. The test adopts a constant potential method, a reaction gas phase product is detected by gas chromatography, a liquid phase product is detected by nuclear magnetic resonance hydrogen spectrum, the coulomb amount corresponding to the concentration of the product 6 is calculated, and the data of selectivity, activity and the like of the catalysis are obtained according to the total coulomb amount recorded by an electrochemical workstation. The measured faradaic efficiencies of the products at different potentials are shown in figure 4, and the measured total current and carbon monoxide bias current densities at different potentials are shown in figure 5.
Example 6:
CO2 electroreduction catalytic performance test of Ni monatomic-nitrogen doped activated carbon nano catalyst by taking CO2 with 20% volume concentration as raw material
The membrane electrode assembly reactor used in example 5 of the present invention and the simulated flue gas components were subjected to a carbon dioxide electroreduction performance test using 20% by volume CO2 and 80% by volume Ar as raw material gases, and the gas flow rate was maintained at 50sccm and the anode potassium hydroxide electrolyte flow rate was maintained at 60mL/h during the test. The test adopts a constant potential method, a reaction gas phase product is detected by gas chromatography, a liquid phase product is detected by nuclear magnetic resonance hydrogen spectrum, coulomb amount corresponding to the product concentration is calculated, and data such as selectivity, activity and the like of the catalysis are obtained according to the total coulomb amount recorded by an electrochemical workstation. The measured faradaic efficiencies of the products at different potentials are shown in figure 6, and the measured total current and carbon monoxide bias current densities at different potentials are shown in figure 7.
Example 7:
CO2 electroreduction catalytic performance test of Ni monatomic-nitrogen doped activated carbon nano catalyst by taking CO2 with 2% volume concentration as raw material
The membrane electrode assembly reactor used in example 2 of the present invention and the simulated flue gas components were subjected to a carbon dioxide electroreduction performance test using 2% by volume CO2 and 98% by volume Ar as raw material gases, and the gas flow rate was maintained at 50sccm and the anode potassium hydroxide electrolyte flow rate was maintained at 60mL/h during the test. The test adopts a constant potential method, a reaction gas phase product is detected by gas chromatography, a liquid phase product is detected by nuclear magnetic resonance hydrogen spectrum, coulomb amount corresponding to the product concentration is calculated, and data such as selectivity, activity and the like of the catalysis are obtained according to the total coulomb amount recorded by an electrochemical workstation. The measured faradaic efficiencies of the products at different potentials are shown in figure 8, and the measured total current and carbon monoxide bias current densities at different potentials are shown in figure 9.
The above embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.
Claims (10)
1. A Ni monatomic-nitrogen-doped carbon nanocatalyst is characterized by comprising nitrogen-doped carbon and Ni atoms which are independently loaded on the surface of a carbon material.
2. The Ni monatomic-nitrogen-doped carbon nanocatalyst of claim 1, wherein the nitrogen-doped carbon comprises, but is not limited to, nitrogen-doped activated carbon black, nitrogen-doped graphite powder, nitrogen-doped graphene, nitrogen-doped carbon nanotubes, and the like.
3. The Ni monatomic-nitrogen-doped carbon nanocatalyst of claim 1 or 2, wherein the mass ratio of Ni atoms to nitrogen-doped carbon is 3 to 4: 95 to 105.
4. The application of the Ni monatomic-nitrogen-doped carbon nanocatalyst as set forth in claim 1, 2 or 3, wherein the catalyst is applied to the reaction for preparing carbon monoxide by electrocatalytic conversion of flue gas.
5. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst according to claim 1, 2 or 3, comprising the steps of: dispersing the activated carbon material in deionized water to obtain a mixed solution A; adding a nickel nitrate solution into the mixed solution A to obtain a mixed solution B; centrifugally collecting the mixed solution B, washing and drying the obtained reaction product to obtain Ni2+-a carbon powder; ni to be prepared2+Carbon powder mixed with urea for high temperature sintering, or Ni prepared2+-carbon powder in NH3Calcining at high temperature in the atmosphere of 75-85 sccm ammonia gas or argon gas at the sintering temperature of 750-850 ℃ for 0.5-1.5 h to obtain the Ni monatomic-nitrogen-doped carbon nano-catalyst, wherein the Ni is2+-the mass ratio of carbon powder to urea is 95-105 (mg): 0.9 to 1.1 (g).
6. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst of claim 5, wherein the mass-to-volume ratio of the activated carbon material to deionized water is 95 to 105 (mg): 30-40 (mL), and the concentration of the nickel nitrate solution is 2.8-3.2 mg/mL.
7. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst according to claim 5 or 6, wherein the adding speed of the nickel nitrate solution is 19 to 21mL/h, the stirring reaction time of the mixed solution B is 6 to 8h, and the rotation speed of the stirrer is 1000 to 1200 rpm.
8. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst according to claim 5 or 6, wherein the washing treatment uses a polar solvent, and the specific operation process of the washing treatment is as follows: and carrying out centrifugal separation on the mixed solution B after reaction, carrying out ultrasonic washing on a product obtained by the centrifugal separation by using a polar solvent, then continuing carrying out the centrifugal separation, and carrying out ultrasonic washing on the product obtained by the centrifugal separation by using the polar solvent, wherein the ultrasonic washing time is 1-2 min each time, the rotating speed of the centrifugal separation is 7000-8000 r/min each time, and the time of the centrifugal separation is 5-7 min each time.
9. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst according to claim 5 or 6, wherein the high-temperature sintering treatment is specifically performed as follows: and putting the mixed sample into a crucible, placing the crucible into a tube furnace for sintering, cooling to room temperature, and collecting the sintered product.
10. The method for preparing the Ni monatomic-nitrogen-doped carbon nanocatalyst according to claim 5 or 6, wherein the carbon material is activated by the following method: dispersing a carbon material in nitric acid for dissolving, performing condensation reflux on the activated carbon material, cooling to room temperature, washing and drying the obtained product to obtain the activated carbon material, wherein the mass-volume ratio of the carbon material to a 9M nitric acid solution is 1.8-2.2 (g): 100(mL), the temperature of condensation reflux is 85-95 ℃, and the time of condensation reflux is 2-4 h.
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