CN109759049B - Method for preparing mesoporous carbon-supported metal monoatomic catalyst - Google Patents
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Abstract
The invention discloses a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps: synthesizing mesoporous carbon by using Zn salt; and removing the template in the mesoporous carbon product to obtain the mesoporous carbon-supported metal monoatomic catalyst. Has the advantages that: the invention uses Zn salt in the carbonization process, and utilizes the evaporation of Zn on the mesoporous carbon carrier in the high-temperature synthesis process to manufacture nano-scale micropores on the mesoporous carbon carrier, so that the mesoporous carbon carrier becomes a hierarchical porous material. The nano-scale micropores not only improve the solute transmission process in the catalysis process, but also provide more active sites for the deposition of metal monoatomic atoms, play a role in anchoring and improve the stability of the monoatomic atoms. The mesoporous carbon-supported metal monatomic catalyst has better catalytic activity because the dispersity and the carrying capacity of the monatomic are improved.
Description
Technical Field
The invention relates to the technical field of new material preparation, in particular to a method for preparing a mesoporous carbon-supported metal monatomic catalyst.
Background
The catalytic technology is used as the basis of modern chemical industry and is increasingly widely applied to industries such as chemistry, petroleum refining, medicine, new energy and the like and environmental protection industries. The enormous success of the modern chemical industry is associated with the use of catalysts. Currently, more than 90% of chemical products are produced by means of catalysts. The supported metal catalyst has excellent catalytic performance, such as high activity, high selectivity or both, and is widely applied to a plurality of important industrial catalytic reactions. The high activity of the supported metal cluster catalyst is attributed to the fact that the metal active component exists in the form of highly dispersed nanoclusters on a carrier with high specific surface area, so that catalytic active sites can be fully utilized, and the reaction activity and the metal atom utilization rate of the catalyst are further improved. Theoretically, the limit of dispersion of supported metal 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.
Since 2011, the monatomic Pt/FeO was prepared from the composition work of academicians under the action of DalianixThe catalyst shows high catalytic activity and stability in CO oxidation and CO selective oxidation reactions, and the monatomic catalyst becomes a new favorite for heterogeneous catalytic research in recent years. The monatomic catalyst has extremely low metal loading capacity, greatly improves the utilization efficiency of metal atoms, and can change the adsorption/desorption selectivity of active components on the catalyst to different molecules, thereby influencing the reaction rate. The research on the preparation of uniformly dispersed single atoms which are used as catalytic active centers provides huge potential for realizing high activity and high selectivity of catalytic reaction.
Disclosure of Invention
The invention aims to provide a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which aims to solve the technical problems that the reaction efficiency is influenced due to high metal loading amount and low metal atom utilization rate in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of making a mesoporous carbon supported metal monatomic catalyst, said method comprising:
synthesizing a mesoporous template;
synthesizing mesoporous carbon by using Zn salt;
and removing the template in the mesoporous carbon product to obtain the mesoporous carbon-supported metal monoatomic catalyst.
Furthermore, the step of synthesizing mesoporous carbon by using Zn salt adopts a hard template method, the mesoporous template is dissolved in water, is uniformly mixed with cane sugar, sulfuric acid, Zn salt and metal salt, is dried and evaporated, is subjected to primary carbonization, and is fully carbonized under the vacuum condition.
Further, the template in the mesoporous carbon product is removed by placing the mesoporous carbon product in an HF solution.
Further, the step of synthesizing mesoporous carbon using a Zn salt is performed once or more.
Further, the mass ratio of the mesoporous template to water is 1: 1-1: 50.
further, the molar mass sum ratio of the Zn salt to the metal salt is 1: 1-1: 100.
further, the mass sum ratio of the sucrose to the Zn salt is 1: 10-1: 0.1.
further, the temperature of the preliminary carbonization is 60-200 DEG CoAnd C, the primary carbonization time is 10-100 hours.
Further, the temperature of the full carbonization is 800-1100 DEG CoAnd C, fully carbonizing for 2-20 hours.
Furthermore, the time required for removing the template in the mesoporous carbon product is 4-20 hours.
Has the advantages that: the invention uses Zn salt in the carbonization process, and utilizes the evaporation of Zn on the mesoporous carbon carrier in the high-temperature synthesis process to manufacture nano-scale micropores on the mesoporous carbon carrier, so that the mesoporous carbon carrier becomes a hierarchical porous material. The nano-scale micropores not only improve the solute transmission process in the catalysis process, but also provide more active sites for the deposition of metal monoatomic atoms, play a role in anchoring and improve the stability of the monoatomic atoms. The mesoporous carbon-supported metal monatomic catalyst has better catalytic activity because the dispersity and the carrying capacity of the monatomic are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern (XRD) of CMK-3 and monatomic Fe-modified CMK-3 catalysts;
FIG. 2 is an SEM surface morphology of CMK-3 and monatomic Fe-modified CMK-3 catalysts; wherein, a is the SEM surface topography of CMK-3, and b is the SEM surface topography of the monoatomic Fe modified CMK-3 catalyst;
FIG. 3 is a HRTEM surface morphology of a monatomic Fe-modified CMK-3 catalyst;
FIG. 4 shows the result of a charge-discharge process test using a monoatomic Fe-modified CMK-3 catalyst as an electrode of a zinc-air battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The invention provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
synthesizing a mesoporous template, wherein the mesoporous template comprises MCM, SBA, MSU and FDU series;
synthesizing mesoporous carbon by using Zn salt, wherein the mesoporous carbon comprises CMK, FDU and OMC series; the step of synthesizing mesoporous carbon by using the mesoporous template is carried out once or for many times;
and removing the template to obtain the mesoporous carbon-supported metal monoatomic catalyst.
The following examples serve to illustrate specific embodiments of the invention:
example one
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, a hard template method is adopted, and the mass ratio of the mesoporous template to water is 1: 1, Zn salt (ZnCl)2) The total molar mass ratio of the metal salt to the metal salt (comprising one or a mixture of two of iron, cobalt, nickel, platinum, ruthenium, gold, silver, palladium, lead and iridium) is 1: 1, the mass sum ratio of the sucrose to the Zn salt is 1: dissolving the mesoporous template in water, uniformly mixing the mesoporous template with cane sugar, sulfuric acid, Zn salt and metal salt, drying and evaporating the mixture, and performing primary carbonization for 10 hours at the temperature of 200 ℃, namely: respectively adding sucrose, sulfuric acid, metal salt and Zn salt solution into a silicon sample containing partial polymer and carbonized sucrose, fully mixing and carbonizing; and then fully carbonizing at 1100 ℃ for 2 hours under vacuum.
And c, magnetically stirring the product obtained in the step b for 4 hours at room temperature by using a hydrofluoric acid (HF) solution with the mass concentration of 1% to remove the template, thereby obtaining the mesoporous carbon-supported metal monatomic catalyst.
Example two
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, a hard template method is adopted, and the mass ratio of the mesoporous template to water is 1: 25, Zn salt (ZnCl)2) The total molar mass ratio of the metal salt to the metal salt (comprising one or a mixture of two of iron, cobalt, nickel, platinum, ruthenium, gold, silver, palladium, lead and iridium) is 1: 50, the mass sum ratio of the sucrose to the Zn salt is 1: 5, dissolving the mesoporous template in water, uniformly mixing the mesoporous template with cane sugar, sulfuric acid, Zn salt and metal salt, drying and evaporating the mixture, and then carrying out primary carbonization for 55 hours at the temperature of 130 ℃, namely: respectively adding sucrose, sulfuric acid, metal salt and Zn salt solution into a silicon sample containing partial polymer and carbonized sucrose, fully mixing and carbonizing; and then fully carbonizing at 950 ℃ for 11 hours under vacuum condition.
And c, magnetically stirring the product obtained in the step b at room temperature for 12 hours by using a hydrofluoric acid (HF) solution with the mass concentration of 10% to remove the template, thus obtaining the mesoporous carbon-supported metal monatomic catalyst.
EXAMPLE III
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, a hard template method is adopted, and the mass ratio of the mesoporous template to water is 1: 50, Zn salt (ZnCl)2) The total molar mass ratio of the metal salt to the metal salt (comprising one or a mixture of two of iron, cobalt, nickel, platinum, ruthenium, gold, silver, palladium, lead and iridium) is 1: 100, the mass sum ratio of the sucrose to the Zn salt is 1: 0.1, dissolving the mesoporous template in water, uniformly mixing with cane sugar, sulfuric acid, Zn salt and metal salt, drying and evaporating the mixture, and then carrying out primary carbonization for 100 hours at the temperature of 60 ℃, namely: respectively adding sucrose, sulfuric acid, metal salt and Zn salt solution into a silicon sample containing partial polymer and carbonized sucrose, fully mixing and carbonizing; and then fully carbonizing at 850 ℃ for 20 hours under vacuum condition.
And c, magnetically stirring the product obtained in the step b for 20 hours at room temperature by using a hydrofluoric acid (HF) solution with the mass concentration of 20% to remove the template, thus obtaining the mesoporous carbon-supported metal monatomic catalyst.
Example four
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: p123 is adopted to synthesize mesoporous molecular sieve SBA-15 as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, 1g of SBA-15 was dissolved in 5g of water with 1.25g of sucrose, 0.14g of sulfuric acid, 0.60g of Zn salt and 0.27g of FeCl using a hard template method3After the mixture is uniformly mixed, the mixture is placed in an oven to be heated for 12 hours at the temperature of 100 ℃, then the temperature is raised to 160 ℃, the temperature is kept for 12 hours, and preliminary carbonization is carried out after the drying and evaporation are finished, namely: a silicon sample containing a part of polymer and sucrose carbide is added with 0.8g of sucrose, 0.09g of sulfuric acid and 0.20g of FeCl3And 0.60g ZnCl2Fully mixing the solution, and then continuously carbonizing at 100 ℃ for 12 hours and 160 ℃ for 12 hours; and then fully carbonizing at 900 ℃ for 5 hours under vacuum condition.
And c, magnetically stirring the mixture for 4 hours at room temperature by using 5 percent hydrofluoric acid, and removing the silicon dioxide template to obtain the hierarchical pore CMK-3 carried monatomic Fe catalyst.
Structural analysis: the structures of the CMK-3 and the monatomic Fe modified CMK-3 catalysts were analyzed by XRD. In fig. 1, the (002) and (101) crystal planes of carbon can be seen at 23 ° and 44 °, indicating that no metallic Fe peaks are present, indicating that no Fe nanoparticles are formed by the method of the present invention.
And (3) observing the surface appearance: the surface morphology of the CMK-3 and the monatomic Fe-modified CMK-3 catalysts was observed using a Scanning Electron Microscope (SEM), and the results are shown in FIGS. 2 a and b, and the HRTEM surface morphology of the monatomic Fe-modified CMK-3 catalysts is shown in FIG. 3. In FIG. 2, the typical rod-like structure of the mesoporous carbon CMK-3 is seen, and the surface of the monoatomic Fe-modified CMK-3 synthesized in FIG. 2 becomes rough, and regular channels are destroyed, resulting in a large number of channels and defects. As a result of observation of the monoatomic species by HRTEM, a uniform dispersion of Fe monoatomic species was observed on the CMK-3 support as shown in FIG. 4. The loading of Fe monoatomic atoms on CMK-3 was 2.41 wt% by ICP. Therefore, by the method provided by the invention, higher load of Fe single atoms can be obtained.
EXAMPLE five
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve MCM-48 by using CTAB as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, 1g of MCM-48 was dissolved in 10g of water with 2.56g of sucrose, 0.14g of sulfuric acid, 2g of Zn salt and 0.47g of CoCl by the hard template method2After the mixture is uniformly mixed, the mixture is placed in an oven to be heated for 10 hours at the temperature of 120 ℃, then the temperature is raised to 140 ℃, the temperature is kept for 10 hours, and preliminary carbonization is carried out after the drying and evaporation are finished, namely: a silicon sample containing a part of the polymer and sucrose carbide was added with 1.8g of sucrose, 0.09g of sulfuric acid, and 0.80g of CoCl2And 2.40g ZnCl2Fully mixing the solution, and then continuously carbonizing at 120 ℃ for 10 hours and 140 ℃ for 10 hours; and then fully carbonizing at 800 ℃ for 10 hours under vacuum condition.
And c, magnetically stirring the mixture for 10 hours at room temperature by using 10 percent hydrofluoric acid, and removing the silicon dioxide template to obtain the hierarchical pore CMK-1 loaded monoatomic Ni catalyst.
EXAMPLE six
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve SBA-15 as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, 1g of SBA-15 was dissolved in 10g of water using a hard template method, and mixed with 1.25g of sucrose, 0.14g of sulfuric acid, 4g of Zn salt and 0.82g of CoCl2、0.87g H2PtCl6After the mixture is uniformly mixed, the mixture is placed in an oven to be heated for 20 hours at the temperature of 80 ℃, then the temperature is raised to 120 ℃, the heat is preserved for 20 hours, and preliminary carbonization is carried out after the drying and evaporation are finished;and then fully carbonizing at 1100 deg.C for 6 hr under vacuum.
And c, magnetically stirring the mixture for 5 hours at room temperature by using 15 percent hydrofluoric acid, and removing the silicon dioxide template to obtain the multi-level pore CMK-2 loaded monatomic Co and Pt catalyst.
EXAMPLE seven
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve MSU-H as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, 1g of MSU-H was dissolved in 20g of water by a hard template method, and mixed with 4.56g of sucrose, 0.14g of sulfuric acid, 8g of Zn salt and 1.87g H2PtCl6After the mixture is uniformly mixed, the mixture is placed in an oven to be heated for 8 hours at the temperature of 120 ℃, then the temperature is raised to 150 ℃ and kept for 10 hours, and preliminary carbonization is carried out after the drying and evaporation are finished, namely: a silicon sample containing a portion of the polymer and sucrose carbide was added with 2.8g of sucrose, 0.09g of sulfuric acid, and 0.90g of 0.90g H2PtCl6And 4g of ZnCl2Mixing the solution, carbonizing at 120 deg.C for 8 hr and 150 deg.C for 10 hr, adding sucrose 2.8g, sulfuric acid 0.09g, and 0.90g H0.90 g2PtCl6And 4g of ZnCl2Fully mixing the solution, and then continuously carbonizing at the temperature of 120 ℃ for 8 hours and at the temperature of 150 ℃ for 10 hours; and then fully carbonizing at 1200 ℃ for 7 hours under vacuum condition.
And C, magnetically stirring the mixture for 6 hours at room temperature by using 20 percent hydrofluoric acid, and removing the silicon dioxide template to obtain the multi-level pore C-MSU-H load monatomic Pt catalyst.
Example eight
The embodiment provides a method for preparing a mesoporous carbon-supported metal monatomic catalyst, which comprises the following steps:
step a, synthesizing a mesoporous template: synthesizing a mesoporous molecular sieve FDU-5 as a mesoporous template;
step b, synthesizing mesoporous carbon by using Zn salt: specifically, 2g of FDU-5 was dissolved in 2g of water using a hard template method, and mixed with 2g of sucrose, 1g of sulfuric acid, 1g of salt of 1gZn and 2g of AuCl2After the mixture is uniformly mixed, the mixture is placed in an oven to be heated for 6 hours at the temperature of 80 ℃, then the temperature is raised to 160 ℃ and kept for 8 hours, and preliminary carbonization is carried out after the drying and evaporation are finished, namely: adding 1g of sucrose, 0.5g of sulfuric acid and 1g of AuCl into a silicon sample containing part of the polymer and the carbonized sucrose2And 0.5g of ZnCl2Fully mixing the solution, and then continuously carbonizing at 80 ℃ for 6 hours and at 160 ℃ for 8 hours; and then fully carbonizing at 900 ℃ for 6 hours under vacuum condition.
And C, magnetically stirring the mixture for 10 hours at room temperature by using 10 percent hydrofluoric acid, and removing the silicon dioxide template to obtain the multi-level pore C-FDU-loaded monoatomic Au catalyst.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A method for preparing a mesoporous carbon supported metal monatomic catalyst, comprising:
synthesizing a mesoporous template;
synthesizing mesoporous carbon by using Zn salt;
removing the template in the mesoporous carbon product to obtain the mesoporous carbon-supported metal monatomic catalyst;
the step of synthesizing the mesoporous carbon by using the Zn salt adopts a hard template method, the mesoporous template is dissolved in water, is uniformly mixed with cane sugar, sulfuric acid, the Zn salt and metal salt, is dried and evaporated, is subjected to primary carbonization, and is mixed with cane sugar, sulfuric acid, the Zn salt and the metal salt again to be fully carbonized under the vacuum condition.
2. The method of claim 1, wherein the template in the mesoporous carbon product is removed by placing the mesoporous carbon product in an HF solution.
3. The method for preparing a mesoporous carbon supported metal monatomic catalyst of claim 1, wherein the step of synthesizing the mesoporous carbon using a Zn salt is performed once or more.
4. The method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1, wherein the mass ratio of the mesoporous template to the water is 1: 1-1: 50.
5. the method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1, wherein the total molar mass ratio of the Zn salt to the metal salt is 1: 1-1: 100.
6. the method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1, wherein the total mass ratio of sucrose to the Zn salt is 1: 10-1: 0.1.
7. the method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1, wherein the preliminary carbonization temperature is 60 to 200 ℃, and the preliminary carbonization time is 10 to 100 hours.
8. The method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1, wherein the temperature for the sufficient carbonization is 800 to 1100 ℃, and the time for the sufficient carbonization is 2 to 20 hours.
9. The method for preparing a mesoporous carbon supported metal monatomic catalyst according to claim 1 or 2, wherein the time required for removing the template from the mesoporous carbon product is 4 to 20 hours.
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