CN114150339B - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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CN114150339B
CN114150339B CN202111369700.4A CN202111369700A CN114150339B CN 114150339 B CN114150339 B CN 114150339B CN 202111369700 A CN202111369700 A CN 202111369700A CN 114150339 B CN114150339 B CN 114150339B
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catalyst
metal
substrate material
carbon dioxide
prepared
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CN114150339A (en
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钟地长
曹长宇
龚云南
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Tianjin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a catalyst, a preparation method and application thereof, wherein the catalyst comprises a substrate material, wherein metal atoms are loaded on the substrate material, and the metal atoms and nitrogen atoms coordinate to form a catalytic active center. The catalyst of the scheme of the invention has excellent electrocatalytic carbon dioxide reduction performance, and the electrocatalytic product is CO, has no liquid-phase product, is single and is easy to collect and enrich; the current is large, and the unit yield is high. The purer product can be obtained without purification, can be used in wide basic application, does not need purification equipment, and saves cost. Compared with other catalysts used in industry, the catalyst has the advantages of simpler and more convenient synthesis, lower cost, better catalytic effect and better stability, is suitable for large-scale industrialized synthesis and application, is more suitable for actual production and use, reduces the emission of carbon dioxide in the atmosphere, and can generate more ecological and social economic benefits.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst and a preparation method and application thereof.
Background
Along with CO 2 The ever increasing emissions have resulted in a number of unprecedented and impending problems. Such as greenhouse effect due to global warming, sea level elevation, etc. Aiming at the problems, china puts forward a carbon reaching peak and a carbon neutralization target, and more attention is paid to how to solve the problems. Many emerging technologies, such as encapsulation storage, chemical fixation conversion and optical and electrical CO 2 Reduction and the like have been proposed to cope with this problem.
Electrocatalytic CO 2 Reduction of CO 2 Catalytic conversion to various fuels and chemicals is a solution to CO 2 A promising approach to excessive emissions and global warming as CO 2 Reduced electrocatalysts have been developed in many different classes, but it is currently generally necessary to use noble metal catalysts (e.g. Pt, ru, ir) to overcome the excessive energy barrier in electrochemical processes. The use of inexpensive transition metals (e.g., fe, co, ni, cu, zn) instead of noble metals is an effective approach to overcome the disadvantages of low abundance, high cost, etc., which limit their large scale use in electrocatalysis. In addition, due to the advantages of readily available raw materials, simple preparation, good conductivity and the like, the carbon-nitrogen material is used for loading transition metal for electrocatalytic CO 2 Reduction is in recent yearsTo investigate the hot spot. However, due to CO 2 Molecular stability, in the reduction of CO 2 Is usually limited by strong chemical bonds, so that CO is activated and converted 2 Molecules are very difficult and therefore have great limitations in practical applications. At present, the development of the technology is limited by high production cost, low activity, poor stability, complex synthesis method and the like of the transition metal catalyst, so that the catalyst with low cost, high activity, high selectivity and high stability is developed for realizing CO 2 The practical application of electrochemical reduction is significant.
The statements made in the background section do not constitute an admission that they are prior art to the present disclosure.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. To this end, the invention proposes a catalyst which has excellent catalytic performance and is stable in material.
The invention also provides a preparation method of the catalyst.
The invention also provides application of the catalyst.
According to one aspect of the present invention, a catalyst is provided that includes a base material having a metal atom supported thereon, the metal atom coordinated with a nitrogen atom to form a catalytically active site.
According to a preferred embodiment of the invention, there is at least the following advantageous effect: the catalyst of the scheme of the invention has excellent catalytic performance, the Faraday efficiency of electrocatalytic reduction of carbon dioxide to carbon monoxide can reach 98%, and the current density can reach 100mA/cm 2 The material has excellent effect and good stability compared with other catalysts, and the current hardly decays after long-time (30 h) electrolysis, and the Faraday efficiency is not obviously reduced, so that the material has excellent stability.
In some embodiments of the invention, the metal atom is selected from transition metal atoms.
In some preferred embodiments of the invention, the transition metal atom is selected from non-noble transition metal atoms. And non-noble transition metal atoms are adopted, so that the raw material cost is reduced.
In some preferred embodiments of the invention, the transition metal atom is selected from at least one of Fe, co, ni, cu or Zn.
In some more preferred embodiments of the invention, the transition metal atom comprises nickel. The nickel element has better electrocatalytic carbon dioxide reduction performance, and the monoatomic nickel can realize 100% of atom utilization rate, so that the catalytic activity property is improved, and therefore, the highly dispersed nickel atoms can improve the electrocatalytic carbon dioxide activity and inhibit the generation of hydrogen.
In some embodiments of the invention, the base material is a conductive base material.
In some preferred embodiments of the present invention, the conductive base material comprises a conductive carbon material.
In some more preferred embodiments of the present invention, the conductive carbon material comprises at least one of conductive carbon black, acetylene black, graphene, graphite alkyne, carbon nanotubes.
According to another aspect of the present invention, there is provided a method for preparing a catalyst, comprising the steps of:
and mixing the metal precursor with a substrate material and a nitrogen-containing compound, and pyrolyzing the mixture in a protective atmosphere to obtain the catalyst.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects: the preparation method is simple and convenient to operate, the raw materials are cheap and easy to obtain, the production cost is low, and the preparation method is suitable for large-scale expansion production.
In some embodiments of the invention, the metal precursor is selected from at least one of a metal oxide, a metal complex, or a metal framework material.
In some preferred embodiments of the invention, the metal precursor comprises a metal complex. Compared with the scheme adopting metal salt in the related art, the metal source adopted by the scheme of the invention has the advantages that the ligand in the complex can play a role in isolation in the pyrolysis process, the spontaneous aggregation of metal atoms in the pyrolysis process is avoided, the generation of metal nano particles is further avoided, the metal loading capacity is improved, and the overall catalytic activity of the catalyst is improved.
In some embodiments of the invention, the metal complex is prepared by reacting a metal salt with a ligand.
In some embodiments of the invention, the metal salt is selected from transition metal salts.
In some preferred embodiments of the invention, the transition metal salt is selected from at least one of Fe, co, ni, cu or Zn salts.
In some preferred embodiments of the invention, the ligand is selected from at least one of adenine, malonic acid, or 1, 10-phenanthroline. Can coordinate with metal ions to form molecular complexes.
In some embodiments of the invention, the base material is a conductive base material.
In some preferred embodiments of the present invention, the conductive base material comprises a conductive carbon material.
In some more preferred embodiments of the present invention, the conductive carbon material comprises at least one of conductive carbon black, acetylene black, graphene, graphite alkyne, carbon nanotubes.
In some more preferred embodiments of the present invention, the conductive carbon material contains conductive carbon black. The conductive carbon black is used as a carbon substrate material, and is uniformly mixed with a metal complex and a nitrogen-containing compound, then high-temperature pyrolysis is carried out in a protective atmosphere, and the ligand of the complex and nitrogen and hydrogen in dicyandiamide are volatilized in a gas form to obtain the nickel catalyst anchored on the carbon black substrate. The conductive carbon black is used as a carbon substrate material, has low cost and wide source, can be directly purchased, has chemical inertness, is not easy to generate electrode reaction, has good conductivity, better dispersibility in electrode liquid, higher surface area, high purity, good compatibility with other materials and the like, and is widely used as a substrate material of a catalytic material. The carbon black adopted by the invention is commercially available conductive carbon black, and has the advantages of good conductivity, high mechanical strength, stability at high temperature and the like.
In some embodiments of the invention, the nitrogen-containing compound is an organic compound.
In some preferred embodiments of the present invention, the nitrogen-containing compound comprises at least one of dicyandiamide, urea, melamine, thiourea.
In some more preferred embodiments of the invention, the nitrogen-containing compound comprises dicyandiamide. Dicyandiamide does not coordinate to metal atoms to form molecular complexes. The method can provide a nitrogen source in the process of forming the single-atom catalyst, and coordinate with metal to form a metal-N catalytic active site; but also plays a role in isolating metal atoms, and avoids aggregation of the metal atoms in the pyrolysis process, thereby avoiding generation of metal nano particles.
In some embodiments of the invention, the protective atmosphere is selected from at least one of a nitrogen atmosphere or an inert gas atmosphere.
In some preferred embodiments of the invention, the inert gas is selected from argon.
In some preferred embodiments of the invention, the mass ratio of the metal precursor to the base material is 5-300:100.
In some more preferred embodiments of the invention, the mass ratio of the metal precursor to the substrate material is below 200:100.
In some preferred embodiments of the invention, the mass ratio of the nitrogen-containing compound to the base material is 20 to 100:1.
In some embodiments of the invention, the pyrolysis temperature is 700 to 1000 ℃.
In some embodiments of the invention, the pyrolysis time is from 1 to 3 hours.
According to a further aspect of the invention, there is also provided the use of a catalyst in the electrochemical reduction of carbon dioxide.
The use according to a preferred embodiment of the invention has at least the following advantages: the catalyst of the scheme of the invention has excellent electrocatalytic carbon dioxide reduction performance, and the electrocatalytic product is CO, has no liquid-phase product, is single and is easy to collect and enrich; the current is large, and the unit yield is high. The purer product can be obtained without purification, can be used in wide basic application, does not need purification equipment, and saves cost. Compared with other catalysts used in industry, the catalyst has the advantages of simpler and more convenient synthesis, lower cost, better catalytic effect and better stability, is suitable for large-scale industrialized synthesis and application, is more suitable for actual production and use, reduces the emission of carbon dioxide in the atmosphere, and can generate more ecological and social economic benefits.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic diagram of the structure of a complex prepared in example 1 of the present invention, in which capital letters represent elements and numerals and lowercase letters represent atomic number numbers;
FIG. 2 is a Transmission Electron Microscope (TEM) image of different precursor loadings of the catalyst prepared in example 1 of the present invention;
FIG. 3 is an X-ray photoelectron spectrum (XPS) of the catalyst prepared in example 1 of the present invention;
FIG. 4 is a Linear Sweep Voltammetry (LSV) plot of the electrocatalytic carbon dioxide reduction for the catalyst prepared as example 1 of the present invention;
FIG. 5 is a graph showing the Faraday effect of electrocatalytic carbon dioxide reduction for the catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph of the electrolytic stability of the electrocatalytic carbon dioxide reduction of the catalyst prepared according to example 1 of the present invention;
FIG. 7 is a nuclear magnetic resonance diagram of an electrolyte after electrolysis of the catalyst prepared in example 1 of the present invention;
FIG. 8 is an XRD pattern of the catalyst prepared in example 2 of the present invention;
FIG. 9 is a LSV plot of the electrocatalytic carbon dioxide reduction for the catalyst prepared in example 2 of the present invention;
FIG. 10 is a graph showing the Faraday effect of electrocatalytic carbon dioxide reduction for the catalyst prepared in example 2 of the present invention;
FIG. 11 is a schematic structural diagram of a complex prepared in example 3 of the present invention.
FIG. 12 is an XRD pattern of the catalyst prepared in example 3 of the invention;
FIG. 13 is a LSV plot of the electrocatalytic carbon dioxide reduction for the catalyst prepared as example 3 of the present invention;
FIG. 14 is a graph showing the Faraday effect of electrocatalytic carbon dioxide reduction for the catalyst prepared in example 3 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the meaning of "about" refers to plus or minus 2%, unless otherwise specified.
Example 1
The catalyst is prepared by taking conductive carbon black as a substrate to load nickel, and the nickel-loaded carbon material is prepared by fully mixing the conductive carbon black serving as the substrate with a nickel complex and dicyandiamide and performing pyrolysis under an inert atmosphere. The specific process is as follows:
(1) Preparation of precursor (Nickel Complex)
Nickel nitrate hexahydrate, adenine and malonic acid are used as raw materials, deionized water self-made in a laboratory is used as a solvent, the reaction is carried out in a three-neck flask, the reaction is heated by a water bath pot, and reflux is carried out by a condensing tube. Respectively dissolving a ligand solution and a salt solution in deionized water, dropwise adding the salt solution into the ligand solution, adjusting the pH of the reaction solution to 6.0 by using sodium hydroxide, reacting the solution at 80 ℃ for 3 hours, finally filtering the green solution, standing and volatilizing the filtrate at room temperature (preferably 15-40 ℃ in the embodiment at about 25 ℃) for three days to obtain light blue crystals. Specifically, 0.2mmol (59.6 mg) of nickel nitrate hexahydrate was dissolved in 3ml of water, 1mmol (106.1 mg) of malonic acid, 0.2mmol (27.4 mg) of adenine was dissolved in 13ml of water, the two solutions were mixed and stirred at 80℃for 2 hours, the pH was adjusted to 6.0 using 0.1mol of sodium hydroxide, and then the solution was volatilized at room temperature, and crystals appeared three days. The crystal is the target product, and the structure is shown in figure 1.
(2) Preparation of carbon black, nickel Complex and dicyandiamide mixtures
100mg of carbon black and a proper amount of nickel complex (5 mg-300mg in this example: 25 mg) are weighed, a large amount of dicyandiamide (2 g-10g in this example: 10 g) is ball-milled uniformly by using a ball mill for 10 hours at a rotational speed of 500rpm/min, and a gray black mixture is obtained.
(3) Preparation of Nickel catalyst
Placing the mixture obtained in the step (2) in a clean porcelain boat, performing high-temperature pyrolysis in a tubular furnace under pure argon, wherein the pyrolysis temperature is 700-1000 ℃ (about 850 ℃ in the embodiment), and the pyrolysis time is 1-3h (about 2h in the embodiment), so as to obtain black powder, and obtaining the nickel catalyst without further treatment.
Example 2
The catalyst is prepared by taking a carbon nano tube as a substrate to load nickel, and the nickel-loaded carbon material is prepared by taking the carbon nano tube as the substrate, fully mixing the carbon nano tube with a nickel complex and dicyandiamide and carrying out pyrolysis under an inert atmosphere. The specific process is as follows:
(1) Preparation of precursor Nickel Complex
Nickel nitrate hexahydrate, adenine and malonic acid are used as raw materials, deionized water self-made in a laboratory is used as a solvent, the reaction is carried out in a three-neck flask, the reaction is heated by a water bath pot, and reflux is carried out by a condensing tube. Respectively dissolving a ligand solution and a salt solution in deionized water, dropwise adding the salt solution into the ligand solution, adjusting the pH value of the reaction solution to 6.0 by using sodium hydroxide, reacting the solution at 80 ℃ for 3 hours, finally filtering the green solution, standing and volatilizing the filtrate at room temperature for about three days to obtain light blue crystals. Specifically, 0.2mmol (59.6 mg) of nickel nitrate hexahydrate was dissolved in 3ml of water, 1mmol (106.1 mg) of malonic acid, 0.2mmol (27.4 mg) of adenine was dissolved in 13ml of water, the two solutions were mixed and stirred at 80℃for 2 hours, the pH was adjusted to 6.0 using 0.1mol of sodium hydroxide, and then the solution was volatilized at room temperature, and crystals appeared three days. The obtained crystal is the target product.
(2) Preparation of carbon nanotubes, nickel complexes and dicyandiamide mixtures
100mg of carbon nano tube and a proper amount of nickel complex (5 mg-300mg, 5mg in this example) are weighed, a large amount of dicyandiamide (2 g-10g, 2g in this example) is ball-milled uniformly by using a ball mill for 10 hours at a rotating speed of 500rpm/min, and a gray black mixture is obtained.
(3) Preparation of Nickel catalyst
Placing the mixture obtained in the step (2) in a clean porcelain boat, performing high-temperature pyrolysis in a tubular furnace under pure argon, wherein the pyrolysis temperature is 700-1000 ℃ (about 700 ℃ in the embodiment), and the pyrolysis time is 1-3h (about 1h in the embodiment), so as to obtain black powder, and obtaining the nickel catalyst without further treatment.
Example 3
The catalyst is prepared by taking a carbon nano tube as a substrate to load copper, and the nickel-loaded carbon material is prepared by taking the carbon nano tube as the substrate, fully mixing the carbon nano tube with a copper complex and dicyandiamide, and carrying out pyrolysis under an inert atmosphere. The specific process is as follows:
(1) Preparation of precursor copper complexes
Copper chloride dihydrate and adenine are used as raw materials, methanol is used as a solvent, the reaction is carried out in a three-neck flask, heating is carried out by using a water bath pot, and reflux is carried out by using a condenser tube. Specifically, copper sulfate pentahydrate (200 mg) was dissolved in 20ml of methanol, adenine (108 mg) was dissolved in a mixed solvent of 20ml of methanol, and then the two solutions were mixed, stirred at 60 degrees centigrade for 1 hour, collected by centrifugation, washed with methanol, and dried in vacuo to obtain the objective product. The structure is shown in fig. 11.
(2) Preparation of carbon nanotubes, copper complexes and dicyandiamide mixtures
100mg of carbon nano tube and a proper amount of copper complex (5 mg-300mg, 300mg in the embodiment) are weighed, a large amount of dicyandiamide (2 g-10g, 10g in the embodiment) is ball-milled uniformly by using a ball mill, the ball milling time is 10h, and the rotating speed is 500rpm/min, so that a gray black mixture is obtained.
(3) Preparation of copper catalysts
Placing the mixture obtained in the step (2) in a clean porcelain boat, performing high-temperature pyrolysis in a tubular furnace under pure argon, wherein the pyrolysis temperature is 700-1000 ℃ (1000 ℃ in the embodiment), and the pyrolysis time is 1-3h (3 h in the embodiment), so as to obtain black powder, and obtaining the copper catalyst without further treatment.
Test examples
The test example tests the micro-morphology, structure, elements, catalytic performance and stability of the catalysts prepared in examples 1 to 3. Wherein:
1. morphology, structure and elemental analysis:
the micro-morphology of the catalyst prepared in example 1 is shown in fig. 2 b. Meanwhile, other supported catalysts are also prepared according to the preparation process, and are shown in figures 2a, c and d (wherein, figure 2a corresponds to a transmission electron microscope image with a precursor supported amount of 5mg, figure 2c corresponds to a transmission electron microscope image with a precursor supported amount of 50mg, and figure 2d corresponds to a transmission electron microscope image with a precursor supported amount of 100 mg). As can be seen from the figure, the catalyst is spheroidal and no distinct particles are seen, indicating that the product is uniformly distributed in an atomic state on the substrate material. TEM images of the products obtained in examples 2 to 3 are similar and are not shown one by one in order to avoid redundancy.
The analysis of the composition of the catalyst prepared in example 1 was performed by XPS, and as shown in FIG. 3, it can be seen from FIG. 3 that the material prepared in the embodiment of the present invention contains a large amount of pyridine nitrogen, and thus, it will have excellent catalytic effect.
Structural analysis of the catalysts prepared in examples 2 and 3 is shown in fig. 8 and 12. As can be seen from the figure, the catalyst with the target structure is prepared by the scheme of the invention, and has no impurity peak, which indicates that the purity is higher.
2. Catalytic performance test:
1) The electrocatalytic carbon dioxide reduction performance test process of the catalysts prepared in examples 1 to 3 was as follows:
the catalyst was prepared as 5mg/mL of an electrode solution consisting of 950. Mu.L of isopropanol solution and 50. Mu.L of naphthol solution. Uniformly dripping the electrode liquid on carbon cloth with the loading capacity of 1mg/cm -2 . CV testing, LSV testing, and electrolysis testing were performed using an H-cell. The electrolyte used was 0.5mol/L KHCO 3 An Ag/AgCl electrode is used as a reference electrode, and a platinum sheet electrode is used as a counter electrode. LSV test was performed under saturated carbon dioxide and saturated argon, respectively, at a scan rate of 5mV/s and a potential window of 0V to-2.0V (vs. RHE, only 0 to-1.2 (or-1.3) V shown in the latter figure). The test results of the catalysts of examples 1 to 3 are shown in fig. 4, 9 and 13, respectively, and it can be seen from the graph that the polarization current of the catalyst prepared by each example in carbon dioxide is obviously higher than that of argon, which indicates that the material has the performance of electrocatalytic carbon dioxide reduction. At the same time, the catalyst prepared in example 1 has a current density of 100mA/cm at about-1.3V 2 。
2) The qualitative measurement method of the electrocatalytic carbon dioxide reduction product comprises the following steps:
the electrolysis is carried out by using an H-type electrolytic cell, the electrolysis mode is selected as BE, and the specific test process is as follows: introducing carbon dioxide into the electrolyte for 30minAs described above, the electrolyte is ensured to be a saturated carbon dioxide solution. The cell is then energized for electrolysis, respectively at different potentials (e.g., (-1.2V), (-1.1V), -1.0V, 0.9V, -0.8V, -0.7V, (-0.6V), etc., where brackets represent that the test was not performed at that potential in some examples). Detection of gas phase products using gas chromatography (shimadzu GC-2012): taking 0.2mL of the cavity gas of the electrolytic cell, injecting the gas chromatograph to obtain chromatogram information, determining the product and yield through the peak position and the peak area, determining the Faraday efficiency through an ideal gas state equation and a Faraday formula, drawing into a histogram, and testing the catalysts prepared in examples 1, 2 and 3 as shown in figures 5, 10 and 14, wherein the lower dark part column represents H 2 The upper light-colored part represents CO 2 . As can be seen from FIG. 5, the highest Faraday efficiency of the catalyst prepared in example 1 for electrocatalytic reduction of carbon dioxide to carbon monoxide is 98%, and the Faraday efficiency of carbon monoxide can reach more than 90% under a wide electrolysis window of-0.7V to-1.1V. As can be seen from FIG. 10, the highest Faraday efficiency of the catalyst prepared in example 2 for electrocatalytic reduction of carbon dioxide to carbon monoxide is 97%, and the Faraday efficiency of carbon monoxide can reach more than 90% under a wide electrolysis window of-0.6V to-1.0V. As can be seen from fig. 14, the catalyst prepared in example 3 electrocatalytic reduction of carbon dioxide to carbon monoxide has a maximum faradaic efficiency of 86%.
3. Stability test
The electrolysis curve and the current information are obtained through the electrochemical workstation, and the result is shown in fig. 6, and it can be seen from the graph that the current is basically unchanged after the catalyst is electrolyzed for 30 hours, and the Faraday efficiency is not obviously attenuated. The liquid phase product was detected using nuclear magnetism and the results are shown in fig. 7. As can be seen from the figure, no liquid phase product was detected, thus indicating a higher product purity without complicated post-treatment. The stability and product detection results of the catalysts prepared in examples 2 to 3 are similar to those shown in FIGS. 6 and 7, and are not shown one by one to avoid redundancy.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (5)

1. A method for preparing a catalyst, characterized by: the method comprises the following steps:
mixing a metal precursor with a substrate material and a nitrogen-containing compound, and pyrolyzing the mixture in a protective atmosphere to obtain the catalyst;
the metal precursor is a metal complex, and the substrate material is selected from conductive carbon black or carbon nano tubes; the metal complex is prepared by reacting metal salt with a ligand; the metal salt is Ni salt, the ligand is adenine and malonic acid, the nitrogen-containing compound is dicyandiamide, the mass ratio of the metal precursor to the substrate material is 5-300:100, and the mass ratio of the metal precursor to the substrate material is lower than 200:100; the mass ratio of the nitrogen-containing compound to the substrate material is 20-100:1;
the pyrolysis temperature is 700 to 1000 ℃, and the pyrolysis time is 1 to 3 hours.
2. The method for preparing a catalyst according to claim 1, wherein: the protective atmosphere is at least one selected from inert gas atmospheres.
3. The method for preparing a catalyst according to claim 2, wherein: the inert gas is selected from argon.
4. A catalyst, characterized in that: the catalyst prepared by the method as claimed in any one of claims 1 to 3, comprising a base material on which metal atoms are supported, the metal atoms being coordinated with nitrogen atoms to form catalytically active centers.
5. Use of the catalyst according to claim 4 in electrochemical reduction of carbon dioxide.
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CN111620311B (en) * 2019-02-28 2022-03-18 中国科学院化学研究所 Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof
CN110302825B (en) * 2019-08-21 2022-06-07 河南师范大学 Preparation method of transition metal-N-C composite electro-catalytic material
CN111545208A (en) * 2020-05-26 2020-08-18 福州大学 Cobalt-nickel bimetallic catalyst and preparation method thereof

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