CN110773152A - Preparation method of carbon-supported 4-coordinated-oxygen manganese atomic-level dispersed catalyst - Google Patents
Preparation method of carbon-supported 4-coordinated-oxygen manganese atomic-level dispersed catalyst Download PDFInfo
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- CN110773152A CN110773152A CN201911078880.3A CN201911078880A CN110773152A CN 110773152 A CN110773152 A CN 110773152A CN 201911078880 A CN201911078880 A CN 201911078880A CN 110773152 A CN110773152 A CN 110773152A
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
Abstract
The invention discloses a preparation method of a carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst, which comprises the steps of mixing soluble manganese metal salt, a soluble carbon source, water and ethanol, and fully dissolving by ultrasonic waves; and drying and precipitating to obtain a catalyst precursor, calcining the catalyst precursor at 600-800 ℃ in an inert atmosphere, carbonizing a carbon source, decomposing metal salt into metal atoms loaded on carbon, and obtaining the carbon-loaded 4-coordinated-oxygen manganese atom-level dispersed catalyst. The method is simple and low in cost.
Description
Technical Field
The invention relates to a catalyst, in particular to a preparation method of a carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst.
Background
The development of the monatomic catalyst can exert the catalytic efficiency of the metal to the maximum extent and reduce the manufacturing cost. Theoretically, the limit of dispersion of supported catalysts is that the metal is uniformly distributed on the support in the form of a single atom, which is not only an ideal state of supported metal catalysts, but also brings the catalytic science into a smaller research scale, namely single atom catalysis. The monatomic catalyst is applied to CO oxidation and selective oxidation, hydrogenation and selective hydrogenation, NO reduction and oxidation, water gas shift, organic synthesis, methanol steam reforming, fuel cells, photoelectrocatalysis, formaldehyde oxidation and the like, so that the preparation of the monatomic metal catalyst becomes an important breakthrough for researchers.
At present, methods for preparing the monatomic catalyst include a coprecipitation method, an impregnation method, an atomic layer deposition method, a reverse Ostwald ripening method, a gradual reduction method and a solid-phase melting method, however, the methods have the problems of complicated procedures, acid washing, high cost and the like, and therefore, a simple universal method for synthesizing the monatomic catalyst needs to be provided.
Disclosure of Invention
The invention aims to overcome the defects of complex process, acid washing, high cost and the like in the development of a monatomic catalyst in the prior art, and provides a preparation method of a carbon-supported 4-coordinated-oxygen manganese atom-level dispersed catalyst.
The invention is realized by the following technical scheme.
A preparation method of a carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst comprises the following steps:
(1) mixing soluble manganese metal salt, a soluble carbon source, water and ethanol to obtain a mixed solution, and fully dissolving the mixture by ultrasonic waves;
the molar ratio of the soluble manganese metal salt to the soluble carbon source is 1: 3-5;
the mass ratio of the soluble manganese metal salt to water is 0.001-0.01 mol: 1L;
the volume ratio of the substance amount of the soluble manganese metal salt to the ethanol is 0.001-0.01 mol: 1L;
(2) drying and separating out the mixed solution obtained in the step (1) to obtain a solid mixture, namely a catalyst precursor;
(3) transferring the catalyst precursor obtained in the step (2) into a porcelain boat, and transferring into a vacuum tube furnace for calcination;
introducing high-purity argon at the speed of 30 ml/min for protection, heating the vacuum tube furnace from room temperature to 600-800 ℃ at the speed of 5 ℃ per min, preserving the heat for 1-4 h, and calcining under the condition of inert atmosphere; in the high-temperature calcination process, carbonizing a carbon source, decomposing metal salt into metal atoms loaded on carbon, and obtaining a carbon-loaded 4-coordinated-oxygen manganese atom-level dispersed catalyst; after calcining and sintering, the vacuum tube furnace is naturally cooled to room temperature, and the product is taken out and ground by the grinding bowl.
The soluble manganese metal salt in the step (1) is manganese nitrate.
The soluble carbon source in the step (1) is anhydrous glucose.
The water in the step (1) is ultrapure water.
In the step (1), soluble manganese metal salt is mixed with water to obtain an aqueous solution, and then ethanol and a soluble carbon source are sequentially added to obtain a mixed solution.
The temperature for drying and precipitating in the step (2) is 30-80 ℃.
The particle size of the product after grinding in the step (3) is less than 1 μm.
The invention provides a preparation method of a carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst, which comprises the steps of mixing soluble metal salt, a soluble carbon source and water to obtain a mixed solution, then drying and separating out to obtain a catalyst precursor, and finally calcining to obtain the carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst. The metal salt and the carbon source are fully mixed in the solution, and are calcined after being dried, so that the carbon source is carbonized, and meanwhile, metal atoms are loaded on carbon, and the method is simple and low in cost. Experimental results show that the method provided by the invention can be used for preparing the carbon-supported 4-coordinated-oxygen manganese atomic-level dispersed catalyst.
Drawings
FIG. 1 is a high magnification scan of example 1;
FIG. 2 is a high angle annular dark field of the scanning transmission electron microscope of example 1;
FIG. 3 is a high resolution transmission image of a scanning transmission electron microscope of example 1;
FIG. 4 is a scanning transmission electron microscope selected area electron diffraction pattern of example 1;
FIG. 5 is a graph of the normalized Mn edge X-ray absorption near-edge structure spectrum of example 1.
Detailed Description
In order to further illustrate the present invention, the following will describe the preparation method of the carbon supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst in detail with reference to the specific examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
synthesizing a carbon-supported 4-coordinated-oxygen manganese atomic-level dispersed catalyst: the method is characterized by being synthesized by taking a manganese nitrate solution (50%) and glucose as precursors through the steps of dissolving, precipitating, calcining and grinding, and specifically comprising the following steps:
(1) 10 microliter of manganese nitrate solution (50%) is measured and put into a beaker, 40 milliliters of ultrapure water is added, ultrasonic treatment is carried out for 5 minutes to ensure that the solution is uniformly dispersed, 40 milliliters of ethanol is added, then 0.144 gram of anhydrous glucose is added, and the obtained mixture is fully dissolved by ultrasonic treatment.
The water and ethanol are used as dispersion media, and can promote the dispersion of soluble metal salt and soluble carbon source to obtain a uniform phase mixed in a molecular state. The ultrasound can further facilitate mixing of the components.
(2) And (3) putting the mixed solution into an oven, drying and separating out at 70 ℃, and volatilizing water and ethanol in the drying and separating out process to obtain a solid mixture, namely a catalyst precursor.
(3) Taking out the dried catalyst precursor, putting the catalyst precursor into a porcelain boat, transferring the porcelain boat into a vacuum tube furnace, introducing high-purity argon at the speed of 30 ml/min for protection, heating the vacuum tube furnace from room temperature to 700 ℃ at the speed of 5 ℃ per min, and preserving the heat for 4 hours. And (3) calcining under the inert atmosphere condition, carbonizing the carbon source in the calcining process, decomposing the metal salt into metal atoms loaded on carbon, and obtaining the carbon-loaded 4-coordinated-oxygen manganese atom-level dispersed catalyst.
Cooling to room temperature in a vacuum tube furnace, taking out the product, and grinding with a bowl, wherein the particle size of the ground product is less than 1 μm.
The carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst prepared in example 1 is shown in FIGS. 1-5, FIG. 1 is a scanning electron microscope high-power scanning image of example 1, and the catalyst can be seen to be in a porous structure; FIG. 2 is a high-angle annular dark field diagram of a scanning transmission electron microscope of example 1, from which it can be seen that Mn atoms are individually dispersed in the bottomThe above step (1); FIG. 3 is a transmission electron microscope high resolution transmission diagram of example 1, FIG. 4 is a transmission electron microscope selected area electron diffraction diagram of example 1, and FIGS. 3 and 4 illustrate that the catalyst of example 1 is amorphous as a whole and no crystal exists inside; FIG. 5 is a graph of normalized Mn edge X-ray absorption near-edge structure spectra for example 1, from which it can be seen that each Mn metal atom in the catalyst of example 1 is bonded to 4O atoms to form Mn-O
4And (5) structure.
Claims (7)
1. A preparation method of a carbon-supported 4-coordinated-oxygen manganese atomic-scale dispersed catalyst comprises the following steps:
(1) mixing soluble manganese metal salt, a soluble carbon source, water and ethanol to obtain a mixed solution, and fully dissolving the mixture by ultrasonic waves;
the molar ratio of the soluble manganese metal salt to the soluble carbon source is 1: 3-5;
the mass ratio of the soluble manganese metal salt to water is 0.001-0.01 mol: 1L;
the volume ratio of the substance amount of the soluble manganese metal salt to the ethanol is 0.001-0.01 mol: 1L;
(2) drying and separating out the mixed solution obtained in the step (1) to obtain a solid mixture, namely a catalyst precursor;
(3) transferring the catalyst precursor obtained in the step (2) into a porcelain boat, and transferring into a vacuum tube furnace for calcination;
introducing high-purity argon at the speed of 30 ml/min for protection, heating the vacuum tube furnace from room temperature to 600-800 ℃ at the speed of 5 ℃ per min, preserving the heat for 1-4 h, and calcining under the condition of inert atmosphere; in the high-temperature calcination process, carbonizing a carbon source, decomposing metal salt into metal atoms loaded on carbon, and obtaining a carbon-loaded 4-coordinated-oxygen manganese atom-level dispersed catalyst; after calcining and sintering, the vacuum tube furnace is naturally cooled to room temperature, and the product is taken out and ground by the grinding bowl.
2. The method for preparing the carbon-supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the soluble manganese metal salt in the step (1) is manganese nitrate.
3. The method for preparing the carbon-supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the soluble carbon source in the step (1) is anhydrous glucose.
4. The method for preparing the carbon-supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the water in the step (1) is ultrapure water.
5. The method for preparing the carbon-supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the step (1) comprises mixing a soluble manganese metal salt with water to obtain an aqueous solution, and then sequentially adding ethanol and a soluble carbon source to obtain a mixed solution.
6. The preparation method of the carbon-supported 4-coordinate-oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the temperature for drying and precipitating in the step (2) is 30-80 ℃.
7. The method for preparing the carbon-supported 4 coordinate oxygen manganese atomic-scale dispersion catalyst according to claim 1, wherein the particle size of the product after grinding in step (3) is less than 1 μm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588708A (en) * | 1985-04-15 | 1986-05-13 | Kansas State University Research Foundation | Bimetallic solvated metal atom dispersed catalysts |
| CN104923275A (en) * | 2015-06-01 | 2015-09-23 | 常州大学 | Method for preparing porous carbon supported metal carbide |
| CN107469855A (en) * | 2017-09-29 | 2017-12-15 | 清华大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal |
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
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- 2019-11-06 CN CN201911078880.3A patent/CN110773152A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588708A (en) * | 1985-04-15 | 1986-05-13 | Kansas State University Research Foundation | Bimetallic solvated metal atom dispersed catalysts |
| CN104923275A (en) * | 2015-06-01 | 2015-09-23 | 常州大学 | Method for preparing porous carbon supported metal carbide |
| CN107469855A (en) * | 2017-09-29 | 2017-12-15 | 清华大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal |
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
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Application publication date: 20200211 |