CN110801838A - Preparation method of monatomic catalyst - Google Patents
Preparation method of monatomic catalyst Download PDFInfo
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- CN110801838A CN110801838A CN201911120998.8A CN201911120998A CN110801838A CN 110801838 A CN110801838 A CN 110801838A CN 201911120998 A CN201911120998 A CN 201911120998A CN 110801838 A CN110801838 A CN 110801838A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
The invention provides a preparation method of a monatomic catalyst, which comprises the following steps: s1) mixing the graphene oxide dispersion liquid with foam transition metal, and drying in a protective atmosphere to obtain a foam metal-graphene oxide material; s2) liquid-phase ultrasonic stripping is carried out on the foam metal-graphene oxide material, and the monatomic catalyst is obtained. Compared with the prior art, the preparation method takes cheap foam transition metal as a metal source, metal atoms on the surface of the foam metal are captured at normal temperature by utilizing the surface dangling bonds of the graphene oxide, the preparation of the monatomic catalyst can be realized, the metal monatomic is uniformly distributed and has good dispersibility, the loading amount of the metal monatomic can be effectively controlled by controlling the number of the surface dangling bonds, meanwhile, the preparation method is simple to operate, the reaction condition is simple and controllable, the cost is low, the production is easy to expand, and the large-scale preparation of the monatomic catalyst can be realized by increasing the area of the foam transition metal and increasing the input amount of the graphene oxide.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a monatomic catalyst.
Background
With the development of nano-catalysis and the progress of characterization technology, researchers find that surface unsaturated coordination atoms are often catalytic active sites, so that the researchers regulate and control the distribution and structure of the surface atoms of the catalyst by controlling the size, morphology and crystal face of the nano-crystals to improve the catalytic performance. When the size of the nanocrystal is reduced to cluster and monatomic, the energy level structure and the electronic structure of the nanocrystal are fundamentally changed, and due to the unique structural characteristics, the monatomic catalyst often shows different activity, selectivity and stability from the traditional nanocatalyst. The monatomic material not only provides an ideal model and a research platform for understanding the mechanism of catalytic reaction from molecular level, but also is expected to become a novel catalyst with industrial catalytic application potential.
The characteristics of maximum atom utilization rate, high catalytic activity and high selectivity of the monatomic catalyst are the reason, and the monatomic catalyst is generally concerned by the science and industry. At present, the literature reports various methods for preparing carbon-supported nitrogen atoms (SACs), such as pyrolysis, wet chemical synthesis, physical and chemical vapor deposition, electrochemical deposition, and ball milling.
While the monatomic catalyst has many advantages, there are some disadvantages, such as when the metal particles are reduced to the monatomic level, the specific surface area is increased sharply, which leads to the sharp increase of the free energy of the metal surface, and with the increase of the loading capacity, the aggregation coupling is easy to occur during the preparation and reaction to form larger clusters, which leads to the deactivation of the catalyst, etc., especially in the process of expanding the production, the uniformity is often occurred, the problems of nanoparticles are existed, which seriously hinders the industrial production and application of the monatomic catalyst, and therefore, the achievement of excellent stability and large loading capacity is a great challenge in the preparation and application process of the monatomic catalyst.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a monatomic catalyst, wherein the monatomic catalyst prepared by the method has uniform metal monatomic distribution and good dispersibility.
The invention provides a preparation method of a monatomic catalyst, which comprises the following steps:
s1) mixing the graphene oxide dispersion liquid with foam transition metal, and drying in a protective atmosphere to obtain a foam metal-graphene oxide material;
s2) liquid-phase ultrasonic stripping is carried out on the foam metal-graphene oxide material, and the monatomic catalyst is obtained.
Preferably, the ratio of graphene oxide to solvent in the graphene oxide dispersion liquid is 1 mg: (1-20) ml.
Preferably, the foam transition metal is subjected to high-temperature treatment in a reducing atmosphere and then mixed with the graphene oxide dispersion liquid.
Preferably, the temperature of the high-temperature treatment is 500-900 ℃; the time of high-temperature treatment is 1-3 h.
Preferably, the reducing atmosphere is a mixed atmosphere of hydrogen and inert gas; the molar ratio of the hydrogen to the inert gas is 1: (5-20).
Preferably, the area of the foam transition metal is 2.5-16 cm2(ii) a The thickness is 1-5 mm.
Preferably, the ratio of the graphene oxide dispersion to the foam transition metal is 1 mL: (2-10) g.
Preferably, the flow rate of the protective atmosphere during the drying in the step S1) is 10 to 200 ml/min.
Preferably, the ultrasonic power during liquid-phase ultrasonic stripping is 500-1000W; the liquid phase ultrasonic stripping time is 1-5 h.
Preferably, the step S1) is specifically: and (3) dropwise and uniformly dropping the graphene oxide dispersion liquid into the foam transition metal, and drying in a protective atmosphere to obtain the foam metal-graphene oxide material.
The invention provides a preparation method of a monatomic catalyst, which comprises the following steps: s1) mixing the graphene oxide dispersion liquid with foam transition metal, and drying in a protective atmosphere to obtain a foam metal-graphene oxide material; s2) liquid-phase ultrasonic stripping is carried out on the foam metal-graphene oxide material, and the monatomic catalyst is obtained. Compared with the prior art, the preparation method takes cheap foam transition metal as a metal source, metal atoms on the surface of the foam metal are captured at normal temperature by utilizing the surface dangling bonds of the graphene oxide, the preparation of the monatomic catalyst can be realized, the metal monatomic is uniformly distributed and has good dispersibility, the loading amount of the metal monatomic can be effectively controlled by controlling the number of the surface dangling bonds, meanwhile, the preparation method is simple to operate, the reaction condition is simple and controllable, the cost is low, the production is easy to expand, and the large-scale preparation of the monatomic catalyst can be realized by increasing the area of the foam transition metal and increasing the input amount of the graphene oxide.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a monatomic catalyst provided by the present invention;
FIG. 2 is a transmission electron micrograph showing spherical aberration correction of an iron monatomic catalyst obtained in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image for spherical aberration correction of a cobalt monoatomic catalyst according to the present invention obtained in example 2;
FIG. 4 is a transmission electron microscope image of spherical aberration correction of a nickel monatomic catalyst obtained in example 3 of the present invention;
FIG. 5 is a transmission electron micrograph showing spherical aberration correction of a copper monatomic catalyst obtained in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a monatomic catalyst, which comprises the following steps: s1) mixing the graphene oxide dispersion liquid with foam transition metal, and drying in a protective atmosphere to obtain a foam metal-graphene oxide material; s2) liquid-phase ultrasonic stripping is carried out on the foam metal-graphene oxide material, and the monatomic catalyst is obtained.
Referring to fig. 1, fig. 1 is a schematic diagram of the synthesis of a monatomic catalyst according to the present invention.
In the present invention, the sources of all raw materials are not particularly limited, and the raw materials may be commercially available or self-made.
In the present invention, the graphene oxide dispersion is preferably prepared according to the following method: ultrasonically dispersing graphene oxide in a solvent to obtain a graphene oxide dispersion liquid; the solvent is preferably an organic solvent, more preferably an alcohol solvent, and even more preferably ethanol; the ratio of the graphene oxide to the solvent is preferably 1 mg: (1-20) ml, more preferably 1 mg: (1-10) ml; in some embodiments provided herein, the ratio of graphene oxide to solvent is preferably 1 mg: 1 ml; in some embodiments provided herein, the ratio of graphene oxide to solvent is preferably 1 mg: 5ml of the solution; in some embodiments provided herein, the ratio of graphene oxide to solvent is preferably 1 mg: 10 ml; in other embodiments provided herein, the ratio of graphene oxide to solvent is preferably 1 mg: 20ml of the solution; the power of the ultrasonic wave is preferably 500-1000W; the time of the ultrasonic treatment is preferably 1-3 hours, and more preferably 1-2 hours.
In the present invention, it is preferable to subject the transition metal foam to a high temperature treatment in a reducing atmosphere; the transition metal in the foam transition metal is preferably one or more of iron, cobalt, nickel, copper, zinc, manganese, chromium and titanium; the area of the foam transition metal is preferably 2.5-16 cm2More preferably 4 to 16cm2(ii) a In some embodiments provided herein, the area of the foamed transition metal is preferably 4cm2(ii) a In some embodiments provided herein, the area of the foamed transition metal is preferably 10cm2(ii) a In other embodiments provided herein, the area of the transition metal foam is preferably 16cm2(ii) a The thickness of the foam transition metal is preferably 1-5 mm, more preferably 1-4 mm, still more preferably 1-3 mm, and most preferably 1-2 mm; the reducing atmosphere is preferably a mixed atmosphere of hydrogen and inert gas; the molar ratio of hydrogen to inert gas is preferably 1: (5-20), more preferably 1: (5-15), and more preferably 1: (5-10); the inert gas is preferably nitrogen and/or argon, more preferably argon; the temperature of the high-temperature treatment is preferably 500-900 ℃, more preferably 600-900 ℃, and further preferably 700-900 ℃; what is needed isThe time of the high-temperature treatment is preferably 1 to 3 hours. The oxide layer on the surface of the foam transition metal can be removed by high-temperature treatment.
Mixing the graphene oxide dispersion liquid with the foam transition metal after high-temperature treatment, preferably, dropwise and uniformly dropping the graphene oxide dispersion liquid into the foam transition metal after high-temperature treatment for mixing; the ratio of the graphene oxide dispersion to the foam transition metal is preferably 1 mL: (2-10) g.
After mixing, drying in a protective atmosphere to obtain a foam metal-graphene oxide material; the protective atmosphere is preferably nitrogen and/or argon; the flow rate of the protective atmosphere during drying is preferably 10-200 ml/min, more preferably 50-200 ml/min, still more preferably 50-150 ml/min, and most preferably 50-100 ml/min; in some embodiments provided herein, the flow rate of the protective atmosphere is preferably 50 ml/min; in some embodiments provided herein, the flow rate of the protective atmosphere is preferably 80 ml/min; in other embodiments provided herein, the flow rate of the protective atmosphere is preferably 100 ml/min. In the process, oxygen-containing dangling bonds on the surface of the graphene oxide and metal atoms on the surface of the foam transition metal are subjected to electron transfer, and metal-oxygen coordination is formed.
Carrying out liquid phase ultrasonic stripping on the foam metal-graphene oxide material to obtain a monatomic catalyst; the solvent used for the liquid phase ultrasonic stripping is preferably an organic solvent, more preferably an alcohol solvent, and further preferably ethanol; the volume of the organic solvent is 500-1000 ml; the ultrasonic power is preferably 500-1000W during liquid phase ultrasonic stripping; the time for liquid phase ultrasonic stripping is preferably 1-5 h.
According to the preparation method, cheap foam transition metal is used as a metal source, metal atoms on the surface of the foam metal are captured at normal temperature by utilizing the surface dangling bonds of the graphene oxide, the preparation of the monatomic catalyst can be realized, the metal monatomic is uniform in distribution and good in dispersity, the loading amount of the metal monatomic can be effectively controlled by controlling the number of the surface dangling bonds, meanwhile, the preparation method is simple to operate, simple and controllable in reaction conditions, low in cost and easy to expand production, and the input amount of the graphene oxide is increased by increasing the area of the foam transition metal, so that the large-scale preparation of the monatomic catalyst can be realized.
In order to further illustrate the present invention, the following will describe the preparation method of a monatomic catalyst according to the present invention in detail with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 ultrasonically dispersing graphene oxide in an ethanol solution, ultrasonically (with the power of 500W) for 2 hours to form a uniform graphene oxide dispersion liquid, wherein the mass-to-volume ratio of the graphene oxide to the ethanol is 1 mg: 1 mL.
1.2 area of 4cm2And the foamed iron with the thickness of 2mm is placed in a tubular furnace, hydrogen/argon mixed gas (the molar ratio is 1: 10) is introduced to remove oxygen, and then under the hydrogen/argon mixed atmosphere, the oxidation layer on the surface of the foamed metal is removed by high-temperature treatment at the temperature of 700 ℃ for 1 h.
1.3, dropwise and uniformly dropping the graphene oxide dispersion liquid into the treated foam iron in the step 1.2 (the ratio of the graphene oxide dispersion liquid to the foam nickel is 1 mL: 5g), and drying under the argon atmosphere at the argon flow rate of 100mL/min to obtain the foam iron-graphene oxide material.
1.4 placing the foamed iron-graphene oxide material obtained in the step 1.3 in 500mL of ethanol, and carrying out ultrasonic stripping to obtain the monatomic catalyst, wherein the ultrasonic power is 1000W, and the time is 1 h.
The monoatomic catalyst obtained in example 1 was characterized by a transmission electron microscope for spherical aberration correction, and the result is shown in fig. 2. As can be seen from fig. 2, the iron monoatomic atoms are uniformly dispersed on the surface of the graphene oxide.
Example 2
2.1 ultrasonically dispersing graphene oxide in an ethanol solution, ultrasonically (with the power of 1000W) for 1h to form a uniform graphene oxide dispersion liquid, wherein the mass-to-volume ratio of the graphene oxide to the ethanol is 1 mg: 5 mL.
2.2 area of 10cm2Foamed cobalt having a thickness of 2mm was placed in a tube furnace, and a hydrogen/argon gas mixture (molar ratio 1: 5) was introduced to remove oxygen, followed by introducing a hydrogen/argon gas mixtureAnd under the atmosphere, removing an oxide layer on the surface of the foam metal by high-temperature treatment at 800 ℃ for 1 h.
And 2.3, dropwise and uniformly dropping the graphene oxide dispersion liquid into the foamed cobalt treated in the step 2.1 (the ratio of the graphene oxide dispersion liquid to the foamed cobalt is 1 mL: 10g), and drying under an argon atmosphere at the argon flow rate of 100mL/min to obtain the foamed metal-graphene oxide material.
2.4 placing the foam metal-graphene oxide material in 500mL of ethanol, and carrying out ultrasonic stripping to obtain the monatomic catalyst, wherein the ultrasonic power is 1000W, and the time is 2 h.
The monoatomic catalyst obtained in example 2 was characterized by a transmission electron microscope for spherical aberration correction, and the result is shown in fig. 3. As can be seen from fig. 3, the cobalt monoatomic atoms are uniformly dispersed on the surface of the graphene oxide.
Example 3
3.1 ultrasonically dispersing graphene oxide in an ethanol solution for 2 hours under the ultrasonic power (800W) to form a uniform graphene oxide dispersion liquid, wherein the mass-to-volume ratio of the graphene oxide to the ethanol is 1 mg: 10 mL.
3.2 area of 16cm2And the foamed nickel with the thickness of 1mm is placed in a tubular furnace, hydrogen/argon mixed gas (the molar ratio is 1: 10) is introduced to remove oxygen, and then under the hydrogen/argon mixed atmosphere, the oxidation layer on the surface of the foamed metal is removed by high-temperature treatment at the temperature of 900 ℃ for 1 hour.
And 3.3, dropwise and uniformly dropping the graphene oxide dispersion liquid into the foamed nickel treated in the step 3.2 (the ratio of the graphene oxide dispersion liquid to the foamed nickel is 1 mL: 5g), and drying under an argon atmosphere at an argon flow rate of 80mL/min to obtain the foamed metal-graphene oxide material.
3.4 placing the foam metal-graphene oxide material in 600mL of ethanol, and carrying out ultrasonic stripping to obtain the monatomic catalyst, wherein the ultrasonic power is 1000W, and the time is 1 h.
The monoatomic catalyst obtained in example 3 was characterized by a transmission electron microscope for spherical aberration correction, and the result is shown in fig. 4. As can be seen from fig. 4, the nickel monoatomic ions are uniformly dispersed on the surface of the graphene oxide.
Example 4
4.1 ultrasonically dispersing graphene oxide in an ethanol solution for 1h under the condition of ultrasonic power of 500W to form a uniform graphene oxide dispersion liquid, wherein the mass-to-volume ratio of the graphene oxide to the ethanol is 1 mg: 20 mL.
4.2 area of 16cm2And 2mm thick copper foam is placed in a tubular furnace, hydrogen/argon mixed gas (the molar ratio is 1: 10) is introduced to remove oxygen, and then under the hydrogen/argon mixed atmosphere, the oxidation layer on the surface of the metal foam is removed by high-temperature treatment at the temperature of 700 ℃ for 3 hours.
And 4.3, dropwise and uniformly dropping the graphene oxide dispersion liquid into the 4.2 treated foamy copper (the ratio of the graphene oxide dispersion liquid to the foamy copper is 1 mL: 10g), and drying under an argon atmosphere at an argon flow rate of 50mL/min to obtain the foam metal-graphene oxide material.
4.4, placing the foam metal-graphene oxide material in 1000mL of ethanol, and carrying out ultrasonic stripping to obtain the monatomic catalyst, wherein the ultrasonic power is 500W, and the time is 5 h.
The monoatomic catalyst obtained in example 4 was characterized by a transmission electron microscope for spherical aberration correction, and the result is shown in fig. 5. As can be seen from fig. 5, the copper monoatomic ions are uniformly dispersed on the surface of the graphene oxide.
Claims (10)
1. A method for preparing a monatomic catalyst, comprising:
s1) mixing the graphene oxide dispersion liquid with foam transition metal, and drying in a protective atmosphere to obtain a foam metal-graphene oxide material;
s2) liquid-phase ultrasonic stripping is carried out on the foam metal-graphene oxide material, and the monatomic catalyst is obtained.
2. The preparation method according to claim 1, wherein the ratio of graphene oxide to solvent in the graphene oxide dispersion liquid is 1 mg: (1-20) ml.
3. The method according to claim 1, wherein the foam transition metal is mixed with the graphene oxide dispersion after being subjected to a high-temperature treatment in a reducing atmosphere.
4. The preparation method according to claim 3, wherein the temperature of the high-temperature treatment is 500 ℃ to 900 ℃; the time of high-temperature treatment is 1-3 h.
5. The production method according to claim 3, wherein the reducing atmosphere is a mixed atmosphere of hydrogen and an inert gas; the molar ratio of the hydrogen to the inert gas is 1: (5-20).
6. The method according to claim 1, wherein the area of the transition metal foam is 2.5 to 16cm2(ii) a The thickness is 1-5 mm.
7. The preparation method according to claim 1, wherein the ratio of the graphene oxide dispersion to the foam transition metal is 1 mL: (2-10) g.
8. The method according to claim 1, wherein the flow rate of the protective atmosphere during the drying in step S1) is 10-200 ml/min.
9. The preparation method according to claim 1, wherein the power of ultrasound during the liquid phase ultrasonic stripping is 500-1000W; the liquid phase ultrasonic stripping time is 1-5 h.
10. The preparation method according to claim 1, wherein the step S1) is specifically: and (3) dropwise and uniformly dropping the graphene oxide dispersion liquid into the foam transition metal, and drying in a protective atmosphere to obtain the foam metal-graphene oxide material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113215597A (en) * | 2021-04-06 | 2021-08-06 | 三峡大学 | Preparation method of defective foam graphene loaded transition metal monatomic catalyst |
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| CN107749483A (en) * | 2017-06-12 | 2018-03-02 | 中国科学技术大学 | A kind of catalyst for hydrogen-air fuel cell cathode material and preparation method thereof |
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| US20060292058A1 (en) * | 2004-07-26 | 2006-12-28 | Woods Hole Oceanographic Institution | Ion stripper device made of carbon nanotubes or fullerenes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113215597A (en) * | 2021-04-06 | 2021-08-06 | 三峡大学 | Preparation method of defective foam graphene loaded transition metal monatomic catalyst |
| CN113215597B (en) * | 2021-04-06 | 2022-04-22 | 三峡大学 | Preparation method of defective foam graphene loaded transition metal monatomic catalyst |
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