CN111672521A - Transition metal monoatomic material and preparation method and application thereof - Google Patents
Transition metal monoatomic material and preparation method and application thereof Download PDFInfo
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- CN111672521A CN111672521A CN202010409398.XA CN202010409398A CN111672521A CN 111672521 A CN111672521 A CN 111672521A CN 202010409398 A CN202010409398 A CN 202010409398A CN 111672521 A CN111672521 A CN 111672521A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 45
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- 238000002360 preparation method Methods 0.000 title abstract description 14
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
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- 150000003841 chloride salts Chemical class 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 13
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
Abstract
The invention discloses a transition metal monoatomic material and a preparation method and application thereof. The material contains an active component and a carrier, wherein the active component is a nickel monoatomic atom, an iron monoatomic atom and/or a cobalt monoatomic atom, the carrier is a fluorine-doped carbon nanosheet, and the nickel monoatomic atom, the iron monoatomic atom and/or the cobalt monoatomic atom are uniformly dispersed on the fluorine-doped carbon nanosheet. The metallic nickel monatomic material has higher activity and stability in the application of preparing carbon monoxide by electrocatalytic dioxyreduction. The preparation method provided by the invention can be used for large-scale preparation in an inert atmosphere, and is very suitable for large-scale and industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a transition metal monoatomic material, and a preparation method and application thereof.
Background
In recent years, with the continuous development and utilization of fossil energy (coal, oil, natural gas), the emission amount of carbon dioxide has increased year by year and has a certain influence on the ecosystem balance. On the other hand, in modern society, energy becomes an indispensable part in both production and life, and the development of human society needs to enhance energy supply, but must also consider reducing carbon emission. The electrocatalytic reduction of carbon dioxide into carbon monoxide, which is an important chemical raw material and can be used for producing hydrocarbon small molecular fuel through Fischer-Tropsch synthesis, plays an important role in economic development. The process of hydrogen production by coupling water in an electrocatalysis mode can realize the in-situ reduction and conversion of carbon dioxide under a mild condition. Researchers believe that clean conversion of carbon dioxide to carbon monoxide can be achieved by using renewable energy sources such as wind or solar power to supply power in the presence of suitable electrocatalytic materials. The previous research on the carbon dioxide electrocatalytic reduction in a heterogeneous system by scientists mainly focuses on the noble metal-based catalyst, and the limitation of the noble metal in the practical application is determined by the rarity of the noble metal. In the case of nickel nanoparticles, scientists found that the (111) crystal is almost inert to electrocatalytic reduction of carbon dioxide due to its strong adsorption of CO. With the progress of the characterization technology, the monatomic catalyst is proposed and developed, and has good activity in the aspects of carbon monoxide oxidation, electrocatalytic oxygen reduction, water electrolysis hydrogen production and the like. Recent related researches show that the transition metal-based monatomic carbon composite material has high selectivity and activity for reducing carbon dioxide, realizes high-efficiency conversion of carbon dioxide into carbon monoxide, and provides a good carrier and an optimal reaction site for dispersion of monatomic active sites.
Due to its unique electronic and geometric structure, monatomic catalysts often exhibit desirable catalytic activity in a number of important chemical reactions. If the monatomic catalyst with 100% atomization can be controllably synthesized, high selectivity of carbon dioxide reduction reaction can be realized, and the generation of side reaction hydrogen evolution can be reduced. However, it is difficult to precisely control the microstructure of the synthesized monatomic catalyst at present because monatomic molecules easily diffuse to form a sub-nanostructure, resulting in a decrease in stability thereof.
Disclosure of Invention
The invention provides a transition metal monoatomic material which contains an active component and a carrier, wherein the active component is a nickel monoatomic atom, an iron monoatomic atom and/or a cobalt monoatomic atom, the carrier is a fluorine-doped carbon nanosheet, and the nickel monoatomic atom, the iron monoatomic atom and/or the cobalt monoatomic atom are uniformly dispersed on the fluorine-doped carbon nanosheet.
According to an embodiment of the invention, the loading of the active component on the transition metal monatomic material is 1 to 10 wt%, such as 2 to 8 wt%, illustratively 3 wt%, 4 wt%, 5 wt%, 5.92%, 5.95%, 6 wt%, 6.12%, 7 wt%, 8 wt%.
According to an embodiment of the present invention, the fluorine-doped carbon nanosheets contain elemental carbon, elemental nitrogen, elemental oxygen, elemental hydrogen, and elemental fluorine.
According to an embodiment of the present invention, the fluorine-doped carbon nanosheets are ultrathin two-dimensional nanosheets. For example, the nanoplatelets have a thickness of 0.5-5nm, such as 0.8-4 nm; illustratively, the thickness may be 0.8nm, 1.0nm, 1.25nm, 1.3nm, 2nm, 3.2 nm. The fluorine-doped carbon nanosheet has a high specific surface area and high conductivity, can sufficiently expose an active component, and is doped in a carbon nanosheet structure, and fluorine has high electronegativity, so that a metal monoatomic atom can be stabilized and the loading amount of the metal monoatomic atom can be increased.
According to an exemplary aspect of the present invention, the transition metal monoatomic material is represented by Ni-SAs @ FNC;
wherein Ni is present in monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Ni single atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets;
the loading of Ni monatomic is 1 to 10 wt%, for example, 5.92 wt%; the fluorine-doped carbon nanosheet is a two-dimensional lamellar structure having a thickness of 0.5-5nm, such as 1.25 nm.
According to an exemplary aspect of the invention, the transition metal monoatomic material is represented by Fe-SAs @ FNC; wherein Fe is present in a monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Fe single atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets.
According to an exemplary aspect of the invention, the transition metal monoatomic material is represented by Co-SAs @ FNC; wherein Co is present in a monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Co monatomic atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets.
The invention also provides a preparation method of the transition metal monoatomic material, which comprises the following steps:
(1) mixing a carbon source, a transition metal salt and fluorine dopant dispersion liquid, and freeze-drying the obtained mixture to obtain a precursor;
(2) and cooling the precursor to room temperature after high-temperature pyrolysis to obtain the transition metal monatomic material.
According to the embodiment of the present invention, in the step (1), the carbon source is a carbon-containing organic substance, and may be one, two or more selected from melamine, dicyandiamide, glucose, sucrose and urea; preferably, the carbon source is selected from one or both of melamine and glucose.
According to an embodiment of the present invention, in step (1), the transition metal salt is selected from one, two or more of nickel-containing, iron-and/or cobalt-containing chloride salt, nitrate, acetate and sulfate; preferably nickel nitrate, nickel chloride, ferric nitrate, ferric chloride, cobalt nitrate and/or cobalt chloride.
According to an embodiment of the present invention, in the step (1), the fluorine dopant may be selected from inorganic substances containing fluorine and/or organic substances containing fluorine, such as at least one of polytetrafluoroethylene, ammonium fluoride, ammonium bifluoride, and the like, and is exemplified by polytetrafluoroethylene.
According to an embodiment of the invention, in step (1), the mass ratio of the carbon source to the transition metal salt may be (30-80):1, for example (40-80):1, exemplified by 40:1, 41:1, 50:1, 60:1, 70:1, 80: 1.
According to an embodiment of the invention, in step (1), the mass ratio of the fluorine dopant dispersion to the carbon source may be (0.5-5):1, for example (1-4):1, exemplified by 1:1, 2:1, 2.9:1, 3:1, 4:1, 5: 1.
According to an embodiment of the present invention, in the step (1), the mass ratio of the carbon source, the transition metal salt and the fluorine dopant dispersion may be (30-80):1 (20-200), for example (40-80):1 (30-150), (40-70):1 (40-120), illustratively 40:1:40, 40:1:80, 40:1:120, 41:1:40, 41:1:80, 41:1:120, 50:1:100, 60:1:120, 70:1:100, 80:1: 80.
According to an embodiment of the present invention, when the carbon source contains two substances, such as melamine and glucose, the mass ratio of the two substances is not particularly limited, and may be, for example, (30-50):1, such as (35-45):1, and is illustratively 40: 1.
According to an exemplary embodiment of the present invention, the carbon source comprises melamine and glucose in a mass ratio of 40: 1.
According to an exemplary embodiment of the present invention, the carbon source is melamine, and the mass ratio of the transition metal salt to the melamine is 1: 40.
According to an exemplary embodiment of the present invention, the carbon source is melamine, and the mass ratio of the fluorine dopant dispersion to the melamine is 1:1, 2:1, and 3: 1.
According to an embodiment of the present invention, in the step (1), the carbon source and the transition metal salt may be dispersed in water, and then the fluorine dopant dispersion may be added thereto and mixed uniformly.
Preferably, the mass to volume ratio of the transition metal salt to water is 1 (80-150) g/ml, such as 1 (100) 130) g/ml, illustratively 1:100g/ml, 1:110g/ml, 1:120g/ml, 1:130 g/ml.
Preferably, the fluorine dopant dispersion needs to be slowly added dropwise.
Preferably, the fluorine dopant is present in the fluorine dopant dispersion in an amount of 50 wt% to 70 wt%, such as 53 wt% to 68 wt%, illustratively 50 wt%, 55 wt%, 60 wt%, 62 wt%, 65 wt%, 70 wt%. Further, the dispersing agent in the fluorine dopant dispersion liquid is deionized water.
Wherein, the dispersing and mixing can be selected from the known methods in the field, such as stirring, ultrasonic and the like. So as to promote the dissolution and dispersion of the materials and obtain uniform dispersion liquid.
According to an embodiment of the present invention, in step (1), the mixture may be flash-frozen in liquid nitrogen before the freeze-drying. Wherein the freeze-drying time may be 12-36h, such as 15-30h, exemplary 20h, 24 h.
According to the technical scheme of the invention, in the step (2), the high-temperature pyrolysis temperature is 500-. Further, the pyrolysis is maintained for a period of time not exceeding 5 hours, for example, 0.5 to 4 hours.
Preferably, the high temperature pyrolysis comprises two pyrolysis stages: the temperature of the first pyrolysis stage is 600-700 ℃, and the time is 0.5-2 h; the temperature of the second pyrolysis stage is 850-. Preferably, the temperature of the first pyrolysis stage is 630-680 ℃ and the time is 1-1.5 h. Preferably, the temperature of the second pyrolysis stage is 880-930 ℃ and the time is 1-1.5 h. Illustratively, the temperature of the first pyrolysis stage is 650 ℃ for 1 h; the temperature of the second pyrolysis stage was 900 ℃ for 1 h.
According to the embodiment of the present invention, in the step (2), the temperature reduction after the high-temperature pyrolysis may be performed by naturally reducing the temperature to room temperature. Further pickling and etching of the product is not required.
According to an embodiment of the present invention, the method for preparing the transition metal monatomic material includes the steps of:
(1) mixing melamine, glucose, transition metal salt and polytetrafluoroethylene dispersion liquid to form a uniform mixture, and freeze-drying the mixture to obtain a precursor;
(2) and cooling the precursor to room temperature after high-temperature pyrolysis to obtain the transition metal monatomic material.
The inventor finds that in the preparation process of the traditional supported monatomic material, metal atoms are easy to agglomerate in the carbonization process of the carrier, so that the metal loading capacity cannot be improved, and the fluorine-doped carrier can inhibit the migration and agglomeration of the metal monatomic through a charge effect due to the strong electronegativity of fluorine. In the preparation method provided by the invention, the obtained carrier has an ultrathin two-dimensional nanosheet structure, has a high specific surface area and high conductivity, can expose active sites in a reaction environment to the maximum extent, is favorable for a catalytic process, and further increases the loading capacity of metal monoatomic atoms on the carrier.
The invention also provides the transition metal monatomic material prepared by the method.
The invention also provides the use of the transition metal monatomic material in carbon dioxide reduction electrocatalysis (reduction of carbon dioxide to carbon monoxide), for example as a carbon dioxide reduction electrocatalyst.
The invention provides a carbon dioxide reduction electrocatalyst which contains the transition metal monoatomic material.
The invention has the beneficial effects that:
(1) the transition metal monatomic material provided by the invention takes a nickel, iron or cobalt metal monatomic as an active component, takes a fluorine-doped ultrathin carbon nanosheet as a carrier, and has a load capacity of 1-10 wt% of the nickel, iron or cobalt metal monatomic in the transition metal monatomic material; meanwhile, the micro-morphology of the material is regulated and controlled by introducing the heteroatom, so that the morphology of the material is uniform.
(2) The invention provides a preparation method of a high-load metal monatomic material synthesized under the assistance of nonmetallic element fluorine with strong electronegativity. Fluorine-containing compounds are used as a doping agent of a carrier to induce and form fluorine-doped ultrathin carbon nanosheets, the morphology of the fluorine-doped ultrathin carbon nanosheets can expose active sites in a reaction environment to the maximum extent, and fluorine is doped in a carbon layer to effectively inhibit migration and aggregation of metal atoms, so that the metal single atom loading capacity of the catalyst is further improved.
In addition, the preparation method has low cost and simple process, and lays a foundation for industrial mass production in practical application.
(3) The transition metal monatomic material provided by the invention can be used as a catalyst and applied to preparation of carbon monoxide by electrocatalysis of carbon dioxide reduction. It has high activity, stability, selectivity and Faraday efficiency, and has outstanding advantages in long-term circulation stability and quality activity.
The selectivity of carbon monoxide can be kept above 90% in the range of-0.67 to-0.97V vs RHE voltage, the best performance is achieved at-0.77V, the selectivity of carbon monoxide is high, and the activity is not attenuated in a constant voltage stability test for 10 hours.
Drawings
FIG. 1 is a powder diffraction (XRD) pattern of the Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 3 is an Atomic Force Microscope (AFM) image of the Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 4 is a Transmission Electron Microscope (TEM) image of the Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 5 is a transmission electron microscopy (AC-HAADF-STEM) image of spherical aberration corrected Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 6 is a graph of the electrocatalytic carbon dioxide reduction performance of the Ni-SAs @ FNC catalyst prepared in example 1.
FIG. 7 is a graph of the 10 hour stability of the electrocatalytic carbon dioxide reduction of the Ni-SAs @ FNC catalyst prepared in example 1.
Fig. 8 is an XRD pattern of the Ni monatomic material synthesized in example 2 and example 3.
FIG. 9 is a powder diffraction (XRD) pattern of the Ni-NPs @ NC catalyst prepared in example 4.
FIG. 10 is a Transmission Electron Microscope (TEM) image of the Ni-NPs @ NC catalyst prepared in example 4.
Fig. 11 is a powder diffraction (XRD) pattern of the different carbonization temperature catalysts prepared in examples 5 and 6.
Fig. 12 is a powder diffraction (XRD) pattern of different transition metal catalysts prepared in example 7.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation method of the nickel monatomic material comprises the following steps:
1) 10g of melamine, 0.25g of glucose and 0.25g of nickel nitrate are weighed and dispersed in 30mL of distilled water, and fully stirred for 20 minutes;
2) slowly dripping 30g of dispersion liquid (the mass content of polytetrafluoroethylene is 60 wt%) of polytetrafluoroethylene in water into the dispersion liquid, continuously stirring for 30min, and uniformly mixing to obtain a mixture;
3) then placing the mixture in liquid nitrogen for quick freezing, and placing the frozen and formed mixture in a freeze dryer for drying for 24 hours to obtain a precursor;
4) the precursor obtained is put in argon atmosphere at 2.5 ℃ for min-1Raising the temperature to 650 ℃ at the heating rate, keeping the temperature for 1h, continuing to raise the temperature to 900 ℃ at the same heating rate, continuing to keep the temperature for 1h, and naturally cooling to room temperature after the temperature is raised to obtain the nickel monatomic material.
In the nickel monatomic material, a fluorine-doped ultrathin carbon nanosheet carries a Ni monatomic, which is recorded as Ni-SAs @ FNC. By the ICP-OES method, the loading amount of Ni atoms in the material was detected to be 5.92 wt%.
FIG. 1 is a powder diffraction (XRD) pattern of Ni-SAs @ FNC prepared in example 1. As can be seen from FIG. 1, the XRD pattern of the synthesized Ni-SAs @ FNC shows only the peak of carbon, indicating that Ni is highly dispersed therein.
FIG. 2 is a Scanning Electron Microscope (SEM) image of Ni-SAs @ FNC prepared in example 1. As can be seen from FIG. 2, the synthesized Ni-SAs @ FNC shows a two-dimensional lamellar structure in the SEM image.
FIG. 3 is an Atomic Force Microscope (AFM) image of Ni-SAs @ FNC prepared in example 1. The AFM image of fig. 3 further confirms that it has an ultra-thin two-dimensional lamellar structure with a thickness of only 1.25 nm.
FIG. 4 is a Transmission Electron Microscope (TEM) image of Ni-SAs @ FNC prepared in example 1. As can be seen from FIG. 4, only an ultra-thin carbon substrate was observed in the TEM image of the synthesized Ni @ SAs @ FNC, confirming that Ni is highly dispersed therein, in which no nanoparticles of Ni element or its compound exist.
FIG. 5 is a transmission electron microscopy (AC-HAADF-STEM) image of Ni-SAs @ FNC prepared in example 1. As can be seen from FIG. 5, the AC-HAADF-STEM of the synthesized Ni-SAs @ FNC shows that Ni is monoatomic dispersed in the synthesized material.
FIG. 6 is a graph of the electrocatalytic carbon dioxide reduction performance of Ni-SAs @ FNC prepared in example 1.
The electrocatalytic carbon dioxide reduction test procedure was as follows: 5mg of example 1Ni-SAs @ FNC was weighed as catalyst and dispersed in 350. mu.L of water, 100. mu.L of ethanol and 50. mu.L of nafion to a homogeneous slurry. The slurry is coated on carbon paper to be used as a working electrode, a platinum net is used as a counter electrode, Ag/AgCl is used as a reference electrode, and constant-voltage electrolysis is carried out for 3600 s. During the electrolysis process, the composition and proportion of the products are analyzed by gas chromatography after multiple sampling.
As can be seen from FIG. 6, the synthesized Ni-SAs @ FNC shows excellent performance in electrocatalytic reduction of carbon dioxide into carbon monoxide, and the product selectivity of more than 90% can be maintained in the voltage range of-0.67 to-0.97V vs RHE. It was shown that the best performance was achieved at-0.77V with a large selectivity for carbon monoxide.
FIG. 7 further demonstrates that no decay in activity occurs in the 10 hour constant pressure stability test. Indicating that it can be used as a catalyst for electrocatalytic carbon dioxide reduction.
Example 2
The procedure of example 1 was followed except that the amount of the polytetrafluoroethylene dispersion used in step 2) was reduced to 20 g.
Example 3
The procedure of example 1 was followed except that the amount of the polytetrafluoroethylene dispersion used in step 2) was reduced to 10 g.
Fig. 8 is an XRD chart of the Ni monatomic materials synthesized in examples 2 and 3, and it can be seen from the XRD charts that the Ni monatomic catalysts synthesized by reducing the amount of polytetrafluoroethylene all showed only a broad peak of carbon and did not show a peak of Ni or its compound. This also indicates that both materials synthesized are monatomic materials and can be used as catalysts for the electrocatalytic reduction of carbon dioxide to carbon monoxide.
Example 4
Following the procedure of example 1, except that no polytetrafluoroethylene was added, the resulting product was designated Ni-NPs @ NC.
Fig. 9 is an XRD pattern of the synthesized material of example 4. As can be seen from the figure, the Ni-NPs @ NC without polytetrafluoroethylene added has obvious characteristic diffraction peak of the Ni simple substance.
FIG. 10 is a TEM image of the Ni-NPs @ NC synthesized in example 4. As can be seen from the figure, the morphology of the nano-carbon tube is in a bamboo-like carbon nano-tube structure, and obvious Ni nano-particles are accompanied. This also indicates that polytetrafluoroethylene plays a crucial role in the formation of ultrathin carbon nanosheets and in promoting the atomization process of Ni nanoparticles.
Example 5
The process of example 1 was followed except that the carbonization temperature in the second stage was adjusted to 800 ℃.
Example 6
The process of example 1 was followed, except that the carbonization temperature in the second stage was adjusted to 1000 ℃.
Figure 11 shows the XRD patterns of the materials synthesized in examples 5 and 6. It is shown that when the carbonization temperature is 800 ℃ (example 5) and 900 ℃ (example 1, fig. 1), both show peaks only with carbon, whereas when it is increased to 1000 ℃, XRD indicates the appearance of peaks with elemental nickel metal, which indicates that the carbonization temperature has an influence on the formation of single atoms.
Example 7
The process of example 1 is followed with the only difference that nickel nitrate in step 1) is replaced by Fe (NO)3)3·9H2And O. The material produced was designated as Fe-SAs @ FNC and had a Fe single atom loading of about 6.12%.
Example 8
The process according to example 1, except thatReplacement of nickel nitrate in step 1) to Co (NO)3)2·6H2And O. The material prepared was designated as Co-SAs @ FNC, with a single Co atom loading of about 5.95%.
The materials obtained in examples 7 and 8 are both monatomic materials. Specifically, XRD of the two metal monatomic materials is shown in fig. 12, and no diffraction peak characteristic to the simple metal is present in the materials. The synthesis method of the transition metal monatomic material has universality. Likewise, the monatomic metallic materials prepared in examples 7 and 8 can also be used for the preparation of carbon monoxide by electrocatalytic carbon dioxide reduction.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A transition metal monatomic material is characterized by comprising an active component and a carrier, wherein the active component is a nickel monatomic, an iron monatomic and/or a cobalt monatomic, the carrier is a fluorine-doped carbon nanosheet, and the nickel monatomic, the iron monatomic and/or the cobalt monatomic are uniformly dispersed on the fluorine-doped carbon nanosheet.
2. The material of claim 1, wherein the loading of the active component on the transition metal monatomic material is 1-10 wt%;
preferably, the fluorine-doped carbon nanosheets contain carbon, nitrogen, oxygen, hydrogen and fluorine;
preferably, the fluorine-doped carbon nanosheets are ultrathin two-dimensional nanosheets. Preferably, the thickness of the nanosheets is 0.5-5 nm.
3. A material according to claim 1 or 2, wherein the transition metal monatomic material is represented by Ni-SAs @ FNC;
wherein Ni is present in monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Ni single atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets;
the load of Ni single atom is 1-10 wt%; the fluorine-doped carbon nanosheet is of a two-dimensional lamellar structure, and the thickness of the fluorine-doped carbon nanosheet is 0.5-5 nm.
4. A material according to claim 1 or 2, wherein the transition metal monatomic material is represented by Fe-SAs @ FNC; wherein Fe is present in a monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Fe single atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets.
5. A material according to claim 1 or 2, wherein the transition metal monatomic material is represented by Co-SAs @ FNC; wherein Co is present in a monoatomic form; SAs @ FNC represents fluorine-doped carbon nanosheets, and Co monatomic atoms are uniformly and highly dispersed on the fluorine-doped carbon nanosheets.
6. A method for producing a transition metal monatomic material according to any one of claims 1 to 5, wherein said method comprises the steps of:
(1) mixing a carbon source, a transition metal salt and fluorine dopant dispersion liquid, and freeze-drying the obtained mixture to obtain a precursor;
(2) and cooling the precursor to room temperature after high-temperature pyrolysis to obtain the transition metal monatomic material.
7. The method according to claim 6, wherein in the step (1), the carbon source is a carbon-containing organic substance selected from one, two or more of melamine, dicyandiamide, glucose, sucrose and urea; preferably, the carbon source is selected from one or both of melamine and glucose;
preferably, in step (1), the transition metal salt is selected from one, two or more of nickel-containing, iron-containing and/or cobalt-containing chloride salt, nitrate, acetate and sulfate; preferably nickel nitrate, nickel chloride, ferric nitrate, ferric chloride, cobalt nitrate and/or cobalt chloride;
preferably, in the step (1), the fluorine dopant may be selected from inorganic and/or organic substances containing fluorine, such as at least one of polytetrafluoroethylene, ammonium fluoride and ammonium bifluoride;
preferably, in the step (1), the mass ratio of the carbon source to the transition metal salt is (30-80): 1;
preferably, in the step (1), the mass ratio of the fluorine dopant dispersion liquid to the carbon source is (0.5-5): 1;
preferably, in the step (1), the mass ratio of the carbon source, the transition metal salt and the fluorine dopant dispersion liquid is (30-80):1 (20-200);
preferably, when the carbon source contains two substances, the mass ratio of the two substances is (30-50): 1;
preferably, in the step (1), the carbon source and the transition metal salt are dispersed in water, and then the fluorine dopant dispersion liquid is added into the water and uniformly mixed;
preferably, the mass volume ratio of the transition metal salt to the water is 1 (80-150) g/ml;
preferably, the mass content of the fluorine dopant in the fluorine dopant dispersion liquid is 50% -70%;
preferably, in step (1), the mixture is flash frozen in liquid nitrogen prior to the freeze-drying.
8. The method as claimed in claim 6 or 7, wherein in the step (2), the pyrolysis temperature is 500-1000 ℃; preferably, the pyrolysis incubation time does not exceed 5 hours;
preferably, the high temperature pyrolysis comprises two pyrolysis stages: the temperature of the first pyrolysis stage is 600-700 ℃, and the time is 0.5-2 h; the temperature of the second pyrolysis stage is 850-;
preferably, in the step (2), the temperature reduction after the high-temperature pyrolysis is carried out by naturally reducing the temperature to room temperature;
preferably, after cooling, the product does not need to be acid washed and etched.
9. Use of a transition metal monatomic material according to any one of claims 1 to 5, in carbon dioxide reduction electrocatalysis, preferably as a carbon dioxide reduction electrocatalyst.
10. A carbon dioxide reducing electrocatalyst, characterized in that the catalyst comprises a transition metal monatomic material according to any one of claims 1 to 5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851322A (en) * | 2020-12-29 | 2021-05-28 | 苏州金宏气体股份有限公司 | Pd monatomic BiFeO3Piezoelectric porous ceramic, preparation method thereof and efficient hydrogen production |
| CN113186508A (en) * | 2021-04-27 | 2021-07-30 | 浙江大学 | Method for simply preparing nickel atomic cluster oxygen evolution catalyst |
| CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
| CN113731463A (en) * | 2021-08-18 | 2021-12-03 | 重庆大学 | Preparation method and application of transition metal monatomic photocatalyst |
| CN113981485A (en) * | 2021-12-07 | 2022-01-28 | 郑州轻工业大学 | Nickel-nitrogen co-doped carbon nanosheet catalyst and preparation method and application thereof |
| CN114086212A (en) * | 2021-12-07 | 2022-02-25 | 河北工业大学 | Preparation method and application of asymmetric coordination monatomic catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529475A (en) * | 2015-12-30 | 2016-04-27 | 中国科学院长春应用化学研究所 | Catalyst with dispersed single platinum atoms and preparation method of catalyst |
| CN109382106A (en) * | 2017-08-03 | 2019-02-26 | 中国科学院大连化学物理研究所 | A kind of electroreduction carbon dioxide catalysis material and its preparation and application |
| CN109999883A (en) * | 2019-04-26 | 2019-07-12 | 陕西科技大学 | A kind of nitrogen-doped carbon loads the preparation method of monatomic catalyst |
| CN110067003A (en) * | 2019-04-22 | 2019-07-30 | 北京航空航天大学 | Monatomic doped graphene material of metal and the preparation method and application thereof |
| CN110148762A (en) * | 2019-06-26 | 2019-08-20 | 桂林电子科技大学 | The carbon material and one of a kind of nitrogen, fluorine and transition metal codope graphene-structured walk carbonization manufacture method |
| WO2020031090A1 (en) * | 2018-08-06 | 2020-02-13 | King Abdullah University Of Science And Technology | Single metal atom or bimetallic alloy heterogeneous catalysts on a carbonaceous support produced by metal precursor deposition on exoelectrogen bacteria and pyrolyzing |
| CN109939717B (en) * | 2019-04-15 | 2020-03-31 | 中国科学院化学研究所 | Nitrogen-doped ultrathin carbon nanosheet-loaded monatomic catalyst and preparation method and application thereof |
-
2020
- 2020-05-14 CN CN202010409398.XA patent/CN111672521A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529475A (en) * | 2015-12-30 | 2016-04-27 | 中国科学院长春应用化学研究所 | Catalyst with dispersed single platinum atoms and preparation method of catalyst |
| CN109382106A (en) * | 2017-08-03 | 2019-02-26 | 中国科学院大连化学物理研究所 | A kind of electroreduction carbon dioxide catalysis material and its preparation and application |
| WO2020031090A1 (en) * | 2018-08-06 | 2020-02-13 | King Abdullah University Of Science And Technology | Single metal atom or bimetallic alloy heterogeneous catalysts on a carbonaceous support produced by metal precursor deposition on exoelectrogen bacteria and pyrolyzing |
| CN109939717B (en) * | 2019-04-15 | 2020-03-31 | 中国科学院化学研究所 | Nitrogen-doped ultrathin carbon nanosheet-loaded monatomic catalyst and preparation method and application thereof |
| CN110067003A (en) * | 2019-04-22 | 2019-07-30 | 北京航空航天大学 | Monatomic doped graphene material of metal and the preparation method and application thereof |
| CN109999883A (en) * | 2019-04-26 | 2019-07-12 | 陕西科技大学 | A kind of nitrogen-doped carbon loads the preparation method of monatomic catalyst |
| CN110148762A (en) * | 2019-06-26 | 2019-08-20 | 桂林电子科技大学 | The carbon material and one of a kind of nitrogen, fluorine and transition metal codope graphene-structured walk carbonization manufacture method |
Non-Patent Citations (3)
| Title |
|---|
| JIAFANG XIE ET.AL: "Metal-free fluorine-doped carbon electrocatalyst for CO2 reduction outcompeting hydrogen evolution", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| RUIXUAN QIN ET.AL: "Strategies for Stabilizing Atomically Dispersed Metal Catalysts", 《SMALL METHODS》 * |
| 朱红林等: "CO2电还原用氮掺杂碳基过渡金属单原子催化剂", 《化学进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851322A (en) * | 2020-12-29 | 2021-05-28 | 苏州金宏气体股份有限公司 | Pd monatomic BiFeO3Piezoelectric porous ceramic, preparation method thereof and efficient hydrogen production |
| CN113186508A (en) * | 2021-04-27 | 2021-07-30 | 浙江大学 | Method for simply preparing nickel atomic cluster oxygen evolution catalyst |
| CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
| CN113731463A (en) * | 2021-08-18 | 2021-12-03 | 重庆大学 | Preparation method and application of transition metal monatomic photocatalyst |
| CN113981485A (en) * | 2021-12-07 | 2022-01-28 | 郑州轻工业大学 | Nickel-nitrogen co-doped carbon nanosheet catalyst and preparation method and application thereof |
| CN114086212A (en) * | 2021-12-07 | 2022-02-25 | 河北工业大学 | Preparation method and application of asymmetric coordination monatomic catalyst |
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