CN110479248B - Preparation method of metal oxide supported monatomic catalyst - Google Patents
Preparation method of metal oxide supported monatomic catalyst Download PDFInfo
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- CN110479248B CN110479248B CN201910761775.3A CN201910761775A CN110479248B CN 110479248 B CN110479248 B CN 110479248B CN 201910761775 A CN201910761775 A CN 201910761775A CN 110479248 B CN110479248 B CN 110479248B
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Abstract
The invention discloses a preparation method of a metal oxide supported monatomic catalyst, which comprises the following steps: the first step is as follows: mechanical ball milling: the noble metal compound is dispersed in the metal oxide by a mechanical ball milling method to obtain a monatomic catalyst precursor, wherein the content of the noble metal is 0.01-5 wt%. The second step is that: and (3) high-temperature roasting: and (3) simply roasting the monatomic catalyst precursor obtained in the first step in the air, and cooling to room temperature to obtain the corresponding monatomic catalyst. The ball mill can make the noble metal compound be uniformly distributed in the oxide carrier in a fully dispersed state, and creates a good condition for the formation and stability of metal monoatomic. The invention has no loss of raw materials in the preparation process, and accords with the concept of green and environmental protection. The invention realizes simple preparation of the metal monatomic material, has good expansibility and reproducibility, and solves the problems of low metal content, few varieties, complex preparation method, high cost, large carrier loss and the like in the prior art.
Description
Technical Field
The invention relates to the technical field of material science and engineering, in particular to a preparation method of a metal oxide supported monatomic catalyst.
Background
The monatomic catalyst has the characteristics of both the active center of a homogeneous catalyst and the stable and easily-separated structure of a heterogeneous catalyst, and is a very important breakthrough for realizing a unified 'big' catalytic theory. Has great application potential in industrial catalysis due to the excellent catalytic performance.
The preparation of the monatomic catalyst firstly needs to consider that isolated monatomic atoms are loaded on a carrier, so as to avoid the agglomeration of metal atoms in the preparation and use processes. Theoretically, two measures can be taken to increase the loading of the monatomic metal and avoid agglomeration: one is to increase the surface area of the support and the other is to enhance the interaction of the metal and the support. Based on the two measures, the preparation method of the monatomic catalyst mainly comprises a coprecipitation method, an impregnation method, a mass separation soft landing method, an atomic layer deposition method and the like.
However, various methods for preparing monatomic catalysts have many drawbacks, such as: (1) the mass separation soft landing method has harsh experimental conditions, higher cost and lower yield, and is not suitable for the large-scale practical production of the monatomic catalyst; (2) the metal leaching method is only suitable for a single specific metal and a carrier, has great limitation, and limits the development and application. (3) In the post-treatment process of the wet chemical method, organic precursors in a system need to be removed, and then a single metal atom tends to aggregate to form a sub-nanometer or even nanometer catalyst. (4) In the coprecipitation method, some metal atoms are buried in a carrier aggregation interface or wrapped in a carrier, and the performance of the monatomic catalyst is greatly reduced. (5) The impregnation method hardly ensures that the metal atoms are uniformly dispersed on the surface of the support in the form of individual atoms. (6) The equipment cost of the atomic layer deposition method is high, and the commercialization process is limited.
Chinese patent CN 109225257A uses a method of depositing single atoms to uniformly load single-dispersed metal atoms on the surface of a nano-substrate material, which can rapidly, efficiently and controllably deposit single atoms. However, the method has high requirements on equipment, high equipment cost and complex operation process, and is difficult to realize industrial application.
US patent US20120004098 a1, which process comprises the steps of preparing a solution containing a catalyst and a promoter, the promoter being present in an amount substantially equal to the catalyst and having an opposite charge; adjusting the pH value of the obtained catalyst and promoter solution according to the surface property of the porous catalyst carrier material; immersing the porous material in the solution; removing the porous material from the solution; drying the porous solution under conditions that prevent capillary effects from transferring from the interior of the support to the exterior of the support; finally, calcining the catalyst at high temperature to obtain the monatomic catalyst. But the method has low universality, needs to add an accelerant, is complex to operate and is difficult to realize industrial production.
Chinese patent CN 109589978A adds a functionalized carbon-based material into an organic solvent A, then dropwise adds an organic lithium reagent into the organic solvent A under an inert atmosphere, and reacts under the inert atmosphere after dropwise adding to obtain an intermediate product, wherein the functionalized carbon-based material is a hydroxyl or/and aminated carbon-based material; (2) dispersing the obtained intermediate product and metal chloride in an organic solvent B under inert atmosphere to react to obtain a mixture of a metal monatomic catalyst and lithium chloride; (3) and (3) purifying the mixture in the step (2) to obtain the metal monatomic catalyst. The method has the characteristics of universality, relatively controllable active sites and the like, but the experimental steps are complicated, the reaction conditions need to be strictly controlled, and the mass production is difficult to realize.
In conclusion, the existing methods for preparing the monatomic catalyst have the defects of small yield, difficulty in industrial production, high cost, expensive equipment cost, complex preparation process, strict condition requirement and the like.
Disclosure of Invention
Based on the characteristics and the defects of the existing preparation methods of a plurality of metal monoatomic catalysts, the invention aims to provide a preparation method of a metal oxide supported monoatomic catalyst, which aims to solve the problems of high cost, complex preparation conditions, large loss of a carrier, low metal content, low preparation amount and the like in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a metal oxide supported monatomic catalyst is characterized in that a metal compound is dispersed in a metal oxide by using a mechanical ball milling method to obtain a monatomic catalyst precursor, and the metal content serving as an active center is 0.01-5% by weight; drying the obtained monatomic catalyst precursor overnight, then placing the monatomic catalyst precursor in oxygen-containing gas flow for roasting, and cooling the monatomic catalyst precursor to room temperature to obtain the corresponding monatomic catalyst.
Preferably, in the preparation method of the metal oxide supported monatomic catalyst, the calcination condition is a temperature of 80 to 1200 ℃ and a calcination time of 1 to 48 hours.
Preferably, in the above method for preparing a metal oxide supported monatomic catalyst, the oxygen-containing gas stream is air or oxygen.
Preferably, in the above method for preparing a metal oxide supported monatomic catalyst, the temperature increase rate at the time of calcination is 1 ℃/min to 30 ℃/min.
Preferably, in the above method for preparing a metal oxide supported monatomic catalyst, the cooling to room temperature is a slow cooling process, and the cooling is allowed to proceed naturally.
Preferably, in the above preparation method of the metal oxide supported monatomic catalyst, the drying overnight is drying in an air-blast drying oven or a vacuum drying oven at a drying temperature of 30 to 120 ℃.
Preferably, in the above preparation method of the metal oxide supported monatomic catalyst, the mechanical ball milling is performed by using a ball mill, the ball milling frequency is 0.1 to 45.0 HZ, and the ball milling condition is one of single-phase operation or bidirectional operation; the time of the mechanical ball milling is 1-72 h, and the rotating speed is 10-586 r/min.
Preferably, in the above preparation method of the metal oxide supported monatomic catalyst, the operation of the mechanical ball milling process is stopped, the catalyst precursor in the ball milling pot is stirred several times by using a plastic spoon, and then the operation is continued.
Preferably, in the preparation method of the metal oxide supported monatomic catalyst, the ball milling tank for mechanical ball milling is an agate tank, the volume of the ball milling tank is 25-5000 mL, the ball milling beads are agate beads, and the radius of the agate beads includes three different sizes of 3mm, 6 mm and 10 mm.
Preferably, in the preparation method of the metal oxide supported monatomic catalyst, the metal oxide is one or a combination of several of iron oxide, zirconium oxide, aluminum oxide, cerium oxide, zinc oxide, manganese oxide, titanium oxide, copper oxide, magnesium oxide and cobalt oxide.
Preferably, in the above method for preparing a metal oxide supported monatomic catalyst, the metal compound is one or a combination of more of ammoplatin nitrate, ammopadium nitrate, ruthenium nitrate, rhodium nitrate, silver nitrate, chloroauric acid, chloroplatinic acid, palladium chloride, ruthenium chloride, rhodium chloride, silver chloride, chloroiridic acid, platinum acetylacetonate, palladium acetylacetonate, nickel oxalate and nickel carbonate.
The preparation method of the invention utilizes the oxide with rich oxygen defect sites to well fix single atoms, thereby effectively preventing the agglomeration of the single atoms. The ball mill can make the noble metal compound be uniformly distributed in the oxide carrier in a fully dispersed state, and creates a good condition for the formation and stability of metal monoatomic. The preparation method utilizes cheap oxide and noble metal compound to carry out simple ball milling, and then the corresponding monatomic catalyst can be obtained by simple calcination in the air, and the preparation process has almost no loss. The preparation method of the metal monatomic catalyst greatly reduces the preparation cost and difficulty, can expand different metal compounds and metal oxide carriers, meets the experimental diversification requirements, and enriches the research of related fields.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention has the advantages of simple and easy operation in the preparation process, low cost, no need of precise and expensive instruments, mechanized production and suitability for industrial production.
2. The invention has no loss of raw materials in the preparation process. And the organic carrier or the metal salt carrier is largely lost during the calcination. Accords with the concept of green environmental protection.
3. The invention can accurately control the ratio of noble metal compound and diluted metal oxide, and realize the controllable preparation of noble metal content (0.01-5 wt%);
4. the invention fully utilizes ball milling and precursor dilution to disperse metal atoms, and has wide application range.
Description of the drawings:
FIG. 1 shows Pt prepared from platinum tetraammine nitrate and iron oxide1/Fe2O3A monoatomic catalyst spherical aberration correction transmission electron microscope AC HAADF-STEM diagram; the rings mark the monoatomic metal;
FIG. 2 is Pd prepared from platinum oxide and iron oxide1/Fe2O3A monoatomic catalyst spherical aberration correction transmission electron microscope AC HAADF-STEM diagram; the rings are labeled as monoatomic metals.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the scope of the examples.
Example 1
0.004 g of platinum tetraammine nitrate and 1 g of iron oxide were mixed and charged into a commercial lidded 50 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot is placed into a planetary ball mill QM3SP4L, the ball milling conditions are set to be that the ball milling pot alternately rotates clockwise and anticlockwise every 1.5 h, the waiting time of the bidirectional shutdown is 0, the frequency is 30 HZ, and the ball milling is carried out for 24 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material. Spherical aberration correction transmission electron microscope as shown in FIG. 1 Pt/Fe2O3As shown.
Example 2
0.0017 g of platinum oxide and 1 g of manganese oxide were mixed and charged into a commercial lidded 50 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot is put into a planetary ball mill QM3SP4L, the ball milling conditions are set to rotate clockwise and anticlockwise alternately every 1.5 h, the waiting time of the bidirectional stop is 0, the frequency is 30 HZ, and the ball milling is carried out for 24 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 3
0.125 g of palladium tetraammine nitrate and 25 g of iron oxide were mixed and charged into a commercial 250 ml agate jar equipped with a lid, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 600 ℃ under the air condition to obtain the corresponding monatomic catalyst material. Spherical aberration correction transmission electron microscope as shown in FIG. 2 Pd1/Fe2O3As shown.
Example 4
0.0425 g of chloroauric acid and 25 g of zirconia were mixed and charged into a commercial 250 ml agate jar with a lid, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 5
0.04 g of platinum acetylacetonate and 10 g of alumina were mixed and charged into a commercial 100 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 6
0.0177 g of nickel oxalate and 10 g of magnesium oxide were mixed and charged into a commercial 100 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot is put into a planetary ball mill QM3SP4L, the ball milling conditions are set to rotate clockwise and anticlockwise alternately every 1.5 h, the waiting time of the bidirectional stop is 0, the frequency is 30 HZ, and the ball milling is carried out for 24 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting the ball-milled solid in a muffle furnace or a tubular furnace at 600 ℃ for 2 hours under the air condition to obtain the corresponding monatomic catalyst material.
Example 7
0.0177 g of rhodium nitrate and 10 g of cerium oxide were mixed and charged into a commercial 100 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30.7 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 400 ℃ under the condition of oxygen flow to obtain the corresponding monatomic catalyst material.
Example 8
0.0017 g of palladium chloride and 1 g of zinc oxide were mixed and charged into a commercial lidded 50 ml agate jar, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30.7 HZ, and ball milling for 48 hours. The machine is stopped for two or three times midway, the ball milling tank is taken out and is stirred uniformly by a plastic spoon, the compacted oxide carrier is loosened, and then the operation is carried out. And putting the ball-milled solid into a porcelain boat, and roasting for 2 hours in a muffle furnace or a tubular furnace at 400 ℃ under the condition of oxygen flow to obtain the corresponding monatomic catalyst material.
Example 9
0.0365 g of nickel carbonate and 25 g of alumina were mixed and charged into a commercial 250 ml agate jar equipped with a lid, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 10
0.0325 g of palladium acetylacetonate and 25 g of copper oxide were mixed and charged into a commercial 250 ml agate jar equipped with a lid, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 11
0.0225 g of ruthenium chloride and 25 g of cobalt oxide were mixed and charged into a commercial 250 ml agate jar equipped with a lid, and 10 beads of 3mm agate and 80 beads of 6 mm agate were added thereto. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. The machine is stopped for two or three times midway, the ball milling tank is taken out and is stirred uniformly by a plastic spoon, the compacted oxide carrier is loosened, and then the operation is carried out. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 12
0.0256 g of chloroiridic acid and 25 g of titanium oxide were mixed and charged into a commercial 250 ml agate jar with a lid, and 10 beads of 3mm agate and 80 beads of 6 mm agate were added thereto. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 13
0.0456 g of rhodium nitrate and 25 g of zirconium oxide were mixed and charged into a commercial 250 ml agate jar equipped with a lid, to which 10 beads of 3mm agate and 80 beads of 6 mm agate were added. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 14
0.0256 g of silver chloride and 25 g of cobalt oxide were mixed and charged into a commercial 250 ml agate jar with a lid, and 10 beads of 3mm agate and 80 beads of 6 mm agate were added thereto. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Example 15
0.0256 g of ruthenium chloride and 25 g of manganese oxide were mixed and charged into a commercial 250 ml agate jar, and 10 beads of 3mm agate and 80 beads of 6 mm agate were added thereto. The ball milling pot was placed in a planetary ball mill QM3SP4L under ball milling conditions of alternating clockwise and counterclockwise rotation every 1.5 h, a two-way stop waiting time of 0, a frequency of 30 HZ, and ball milling for 48 hours. Stopping the machine for two or three times, taking out the ball milling tank, uniformly stirring the ball milling tank by using a plastic spoon, loosening the compacted oxide carrier, and then operating. And putting the ball-milled solid into a porcelain boat, and roasting for 5 hours in a muffle furnace or a tubular furnace at 400 ℃ under the air condition to obtain the corresponding monatomic catalyst material.
Claims (3)
1. A preparation method of a metal oxide supported monatomic catalyst is characterized in that a metal compound is dispersed in a metal oxide by a mechanical ball milling method to obtain a monatomic catalyst precursor, wherein the metal content serving as an active center is 0.01-5% by weight; drying the obtained monatomic catalyst precursor overnight, then placing the monatomic catalyst precursor under oxygen-containing gas flow for roasting, and cooling the monatomic catalyst precursor to room temperature to obtain a corresponding monatomic catalyst;
the roasting condition is 400-1200 ℃, and the roasting time is 1-48 hours;
the heating rate during roasting is between 1 ℃/min and 30 ℃/min;
the process of cooling to room temperature is a slow cooling process, and natural cooling is waited;
the drying overnight is drying in a forced air drying oven or a vacuum drying oven, and the drying temperature is 30-120 ℃;
the mechanical ball milling adopts a ball mill, the ball milling frequency is 0.1-45.0 HZ, and the ball milling condition is one of single-phase operation or bidirectional operation; the time of the mechanical ball milling is 1-72 h, and the rotating speed is 10-586 r/min;
stopping operation in the mechanical ball milling process, turning over the catalyst precursor in the ball milling tank for a plurality of times by using a plastic spoon, and then continuing to operate;
the ball milling tank of the mechanical ball milling is an agate tank, the volume of the ball milling tank is 25-5000 mL, the ball milling beads are agate beads, and the radius of the agate beads comprises three different sizes of 3mm, 6 mm and 10 mm.
2. The method of claim 1, wherein the metal oxide is selected from the group consisting of iron oxide, zirconium oxide, aluminum oxide, cerium oxide, zinc oxide, manganese oxide, titanium oxide, copper oxide, magnesium oxide, and cobalt oxide.
3. The method for preparing a metal oxide supported monatomic catalyst of claim 1, wherein the metal compound is one or a combination of more of ammoplatin nitrate, ruthenium nitrate, rhodium nitrate, silver nitrate, chloroauric acid, chloroplatinic acid, palladium chloride, ruthenium chloride, rhodium chloride, silver chloride, chloroiridic acid, platinum acetylacetonate, palladium acetylacetonate, nickel oxalate, and nickel carbonate.
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| CN111330595B (en) * | 2020-04-17 | 2021-04-30 | 天津大学 | Iron oxide loaded monatomic Pd and Pt catalyst, preparation method thereof and application thereof in selective hydrogenation reaction |
| CN111569867A (en) * | 2020-04-20 | 2020-08-25 | 北京邮电大学 | Method for preparing supported noble metal VOCs degradation catalyst by ball milling method |
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| CN111715239A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of oxide-supported monatomic catalyst |
| CN113967478B (en) * | 2020-07-22 | 2023-02-24 | 中国科学院大连化学物理研究所 | High-thermal-stability ruthenium monatomic catalyst and preparation method thereof |
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