CN109759133B - Atom dispersed composite material, preparation method and application thereof - Google Patents
Atom dispersed composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an atom-dispersed composite material, which comprises sulfur-doped mesoporous carbon and metal atoms loaded on the surface of the sulfur-doped mesoporous carbon, wherein the metal atoms and sulfur in the mesoporous carbon form coordination bonds. The application also provides a preparation method of the atom dispersed composite material. The application also provides application of the atom dispersed composite material in hydrogenation catalysis. The composite material with dispersed atoms is synthesized by regulating the type and temperature of the metal salt, and the load capacity of metal atoms in the composite material can reach 10 wt%; the method has universality, is simple to operate, has low cost and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an atom dispersed composite material, a preparation method and application thereof.
Background
In recent years, an atom dispersion catalyst (or a monoatomic catalyst) has been favored by a wide variety of scientific researchers, and exhibits extremely high catalytic activity and selectivity in the catalytic field due to its special atomic size and electronic effect. Compared with a nano-sized metal particle catalyst, the atom dispersion catalyst can realize the maximum utilization of metal, and particularly for a noble metal catalyst, the atom dispersion can greatly reduce the cost. However, as the metal particles are reduced to atomic size, the free energy of the metal surface increases dramatically, leading to a tendency for the metal atoms to agglomerate during preparation or reaction, and thus the metal loading of atom dispersed catalysts reported to date is mostly controlled below 2.0 wt%.
The atomic layer deposition method deposits metal on a carrier layer by layer in an atomic film mode in a self-limiting mode, can control the metal loading capacity by accurately regulating and controlling deposition parameters, has good repeatability, and is widely applied to the preparation of monatomic catalysts. However, the method is expensive in equipment and limited in catalyst synthesis amount, and cannot be applied to industrial production. Although the traditional impregnation method is simple to operate and easy to realize industrial production, the atomic dispersion catalyst prepared by the method is easy to agglomerate, the stability of the catalyst is usually realized by sacrificing the metal loading capacity, and the application field of the catalyst is greatly limited.
Disclosure of Invention
The invention aims to provide a composite material of metal atoms with high load capacity and a preparation method thereof.
In view of the above, the present application provides an atom dispersed composite material, including sulfur-doped mesoporous carbon and metal atoms supported on the surface of the sulfur-doped mesoporous carbon, wherein the metal atoms form coordination bonds with sulfur in the mesoporous carbon.
Preferably, the loading amount of the metal atoms is 1 to 10 wt%.
Preferably, the metal atom is formed of Fe, Co, Ni, Cu, Ru, Pd, Rh, Pd, Re, Os, Ir, Pt or Au.
The application also provides a preparation method of the atom dispersed composite material, which comprises the following steps:
mixing sulfur-doped mesoporous carbon, metal salt and a solvent, and drying to obtain an initial mixture;
carrying out heat treatment on the initial mixture to obtain an atom dispersed composite material; the temperature of the heat treatment is 150-600 ℃.
Preferably, the preparation method of the sulfur-doped mesoporous carbon comprises the following steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
Preferably, the sulfur-containing organic small molecule is 2, 2' -bithiophene, and the transition metal salt is selected from cobalt nitrate hexahydrate; the sulfur-containing small molecule, SiO2The mass ratio of the small balls to the transition metal salt is 2:2: 1; the calcining temperature is 600-900 ℃.
Preferably, the metal element in the metal salt is selected from Fe, Co, Ni, Cu, Ru, Pd, Rh, Pd, Re, Os, Ir, Pt or Au.
Preferably, the heat treatment is performed in an atmosphere of argon, helium or a hydrogen mixture; the hydrogen gas mixture is selected from a mixture of hydrogen and helium or a mixture of hydrogen and argon; the gas flow rate of the atmosphere is 50-500 mL/min.
Preferably, the heating rate of the heat treatment is 1-20 ℃/min.
The application also provides the application of the atom dispersed composite material or the preparation method of the atom dispersed composite material in hydrogenation catalysis.
The application provides an atom-dispersed composite material, which comprises sulfur-doped mesoporous carbon and metal atoms loaded on the surface of the sulfur-doped mesoporous carbon, wherein the metal atoms form coordination bonds with sulfur in the mesoporous carbon; the metal atoms in the atom-dispersed composite material are loaded on the surface of sulfur-doped mesoporous carbon, and metal bonds are not formed among the metal atoms, but form coordination bonds with sulfur, so that agglomeration is avoided, and the highest loading can reach 10 wt%.
The application also provides a preparation method of the atomic dispersion composite material, which comprises the steps of mixing the sulfur-doped mesoporous carbon, the metal salt and the solvent, drying to obtain an initial mixture, and performing heat treatment on the initial mixture to obtain the atomic dispersion composite material; the sulfur-doped mesoporous carbon has a good metal fixing effect, metal atoms and sulfur form metal-sulfur coordination bonds, and the agglomeration of the metal atoms is inhibited; meanwhile, by adjusting the heat treatment temperature, metal atoms are stably loaded on the surface of the sulfur-doped mesoporous carbon.
On the other hand, the preparation method of the atom dispersed composite material has universality for most metals, can be used as a catalyst for hydrogenation catalysis, and has unique activity and stability.
Drawings
FIG. 1 is a high angle annular dark field image-scanning transmission electron microscope (HAADF-STEM) electron micrograph of 10 wt% Pt/SC prepared in example 1 of the present invention;
FIG. 2 is an extended X-ray absorption fine structure (EXAFS) characterization of 10 wt% Pt/SC prepared in example 1 of the present invention;
FIG. 3 is an HAADF-STEM electron micrograph of 10 wt% Ir/SC prepared in example 2 of the present invention;
FIG. 4 is an EXAFS characterization of 10 wt% Ir/SC prepared in example 2 of the present invention;
FIG. 5 is an electron micrograph of HAADF-STEM of 5 wt% Rh/SC prepared in example 3 of the present invention;
FIG. 6 is an EXAFS characterization of 5 wt% Rh/SC prepared in example 3 of the present invention;
FIG. 7 is an electron micrograph of HAADF-STEM of 5 wt% Ru/SC prepared in example 4 of the present invention;
FIG. 8 is an EXAFS characterization of 5 wt% Ru/SC prepared according to example 4 of the present invention;
FIG. 9 is an electron micrograph of HAADF-STEM of 5 wt% Pd/SC prepared in example 5 of the present invention;
FIG. 10 is an EXAFS characterization of 5 wt% Pd/SC prepared in example 5 of the present invention;
FIG. 11 is a comparative graph of the hydrogenation activity of quinoline provided in example 10 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the current situation that an atom dispersed composite material is easy to agglomerate and has a low loading rate, the application provides an atom dispersed composite material and a preparation method thereof, metal atoms in the atom dispersed composite material are stably loaded on the surface of sulfur-doped mesoporous carbon, and metal-sulfur coordination bonds are formed between sulfur and metal, so that the agglomeration of the metal atoms are effectively inhibited, and the loading rate of the metal atoms on the surface of the sulfur-doped mesoporous carbon (SC carrier) is high. Specifically, the embodiment of the invention discloses an atom-dispersed composite material, which comprises sulfur-doped mesoporous carbon and metal atoms loaded on the surface of the sulfur-doped mesoporous carbon, wherein the metal atoms and sulfur in the mesoporous carbon form coordination bonds.
For the atom dispersed composite material provided herein, it comprises sulfur-doped mesoporous carbon as a carrier of metal atoms and metal atoms, which are metal atoms formed by a single metal element that form coordinate bonds with sulfur in the sulfur-doped mesoporous carbon.
The sulfur-doped mesoporous carbon described herein may be prepared according to methods well known to those skilled in the art, and is not particularly limited in this application. According to the invention, the metal atoms are formed from the following metal elements: fe. Co, Ni, Cu, Ru, Pd, Rh, Pd, Re, Os, Ir, Pt or Au. The loading amount of the metal atoms is 1-10 wt%, and in a specific embodiment, the loading amount of the metal atoms is also 5-8 wt%. In the present application, the metal atoms in the atom-dispersed composite are supported on the surface of the sulfur-doped mesoporous carbon, which form metal-sulfur coordination bonds with sulfur in the sulfur-doped mesoporous carbon.
The application also provides a preparation method of the atom dispersed composite material, which comprises the following steps:
mixing sulfur-doped mesoporous carbon, metal salt and a solvent, and drying to obtain an initial mixture;
carrying out heat treatment on the initial mixture under a reducing atmosphere to obtain an atom-dispersed composite material; the temperature of the heat treatment is 150-600 ℃.
The atomic dispersion composite material provided by the application can be prepared by adopting a dipping and heat treatment mode, the method has universality on various metals, and the process operation is simple and easy to implement.
Specifically, in the process of preparing the atomic dispersion composite material, firstly, sulfur-doped mesoporous carbon, metal salt and a solvent are mixed, and an initial mixture is obtained after drying; the process is a mixing process of sulfur-doped mesoporous carbon and metal salt; the preparation method of the sulfur-doped mesoporous carbon is as follows, and more specifically, the preparation method of the sulfur-doped mesoporous carbon comprises the following steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
In the above process of preparing sulfur-doped mesoporous carbon, the sulfur-containing organic small molecule is selected from sulfur-containing small molecules well known to those skilled in the art, and in the present application, the sulfur-containing small molecule is selected from 2, 2' -bithiophene; the transition metal salt is also selected from transition metal salts well known to those skilled in the art, illustratively, in this application the transition metal salt is selected from cobalt nitrate hexahydrate and the solvent may be selected from tetrahydrofuran. The sulfur-containing small molecule, SiO2Pellets and transitionsThe mass ratio of the metal salt is 2:2: 1; the calcining temperature is 600-900 ℃. The above-mentioned sulfur-doped mesoporous carbon may be prepared according to a method well known to those skilled in the art, and the present application is not particularly limited thereto. And in the subsequent etching process, sodium hydroxide is used for etching away silicon dioxide in the carbon material, sulfuric acid is used for etching away metal particles in the carbon material, the two processes are sequentially carried out so as to respectively realize the etching of the silicon dioxide and the metal particles, and finally the sulfur-doped mesoporous carbon is obtained.
For another raw material metal salt in which the metal element is a metal element well known to those skilled in the art, the metal salt described herein may include an organic metal salt or an inorganic metal salt. The salt form of the metal salt is also not particularly limited, and may be a salt form well known to those skilled in the art; in the case of Pt, the salt of Pt may be H2PtCl6、Pt(acac)2、Pt(NH3)4Cl2… … are provided. There is no proportionality for different metal salts, and the addition is reasonable according to the loading of the metal salts in the sulfur-doped mesoporous carbon.
In the process of obtaining the initial mixture, the solvent may be added by selecting a suitable solvent according to the kind of the metal salt precursor, for example, the metal salt is an inorganic metal salt (H)2PtCl6·6H2O) usually water as solvent, and organic metal salts usually ethanol as solvent; in this process, the solvent is mainly intended to be sufficiently miscible and not to undergo chemical reactions.
According to the invention, after the initial mixture has been obtained, it is then subjected to a heat treatment to obtain an atom-dispersed composite material; the process is a reduction process of metal salt, and the metal salt can be reduced by hydrogen in an atmosphere containing hydrogen and also can be reduced under the action of a carbon carrier at a relatively high temperature in an inert atmosphere. The specific process is as follows:
transferring the initial mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, taking inert atmosphere or hydrogen mixed gas as reducing atmosphere, heating to 150-600 ℃ at the speed of 1-20 ℃/min, preserving heat for 1-5 hours, and naturally cooling to room temperature; during this process, the pressure inside the tube furnace was kept constant. The inert atmosphere is argon or helium; the hydrogen gas mixture is selected from a mixture of hydrogen and helium (the content of hydrogen is 3-10 vol%) or a mixture of 3-10 vol% hydrogen and argon (the content of hydrogen is 3-10 vol%). In the process, the speed is 2-15 ℃/min in the specific embodiment; too fast a rate of temperature rise causes the metal element to form metal particles. The temperature of the heat treatment depends on the type of metal precursor, for example, noble metals can be reduced below 200 ℃; in an inert atmosphere, such as argon or helium, higher temperatures are often required to ensure complete ligand removal.
The composite material with the dispersed atoms is prepared by using a dipping and heat treatment mode, the stability of the catalyst is improved by coordination of metal atoms and sulfur atoms on the carrier, and meanwhile, the high-content sulfur on the carrier can realize the high loading capacity of the metal.
The atom-dispersed composite material provided by the application can be used as a catalyst for hydrogenation catalysis, and particularly can be used as a catalyst for quinoline reaction; the catalyst shows unique activity and high stability.
In order to further understand the present invention, the following examples are provided to illustrate the atomic dispersed composite material, the preparation method and the application thereof, and the scope of the present invention is not limited by the following examples.
Example 1
a. 1g of 2, 2' -bithiophene, 1g of SiO2，0.5g Co(NO3)2·6H2Dispersing O in THF, stirring for 6-8 h, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a corundum crucible, putting the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 2 hours, and naturally cooling to room temperature to obtain a carbon material-1;
b. putting the obtained carbon nano material-1 into a conical flask, adding 100-150 mL of 2M NaOH solution, stirring for 36-48 h for primary alkali etching, and filtering to obtain a filter cake; carrying out secondary alkali etching on the filter cake according to the operation, filtering and drying at 80 ℃ to obtain a carbon nano material-2;
c. placing the obtained carbon nano material-2 in a 250mL round-bottom flask, adding 100mL of 0.5mol/L sulfuric acid solution, carrying out acid etching at 90 ℃ for 6-8 h, carrying out suction filtration washing to neutrality, and drying to obtain an SC carrier;
d. putting the obtained 90mg SC carrier and chloroplatinic acid solution containing 10mg of metal platinum into a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
e. the obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 250-300 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-4 h; naturally cooling to room temperature to obtain the atomically dispersed 10 wt% Pt/SC catalyst.
FIG. 1 is the HAADF-STEM characterization of the 10 wt% Pt/SC catalyst prepared in example 1 of the present invention, and it is seen from the picture that the platinum metal is atomically dispersed on the SC support, and the presence of platinum particles is not found.
FIG. 2 is an EXAFS characterization of the 10 wt% Pt/SC catalyst prepared in example 1 of the present invention, from which it can be seen that metallic platinum exists mainly in the form of Pt-S coordination, and no Pt-Pt bond is found.
Example 2
The synthesis procedure for the SC support is the same as in example 1, steps a-c;
b. putting the obtained 90mg SC carrier and iridium chloride solution containing 10mg iridium into a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, introducing pure Ar gas, heating the tube furnace to 400-600 ℃ at the speed of 5-10 ℃/min, and keeping the temperature for 1-4 h; naturally cooling to room temperature to obtain the atom dispersed 10 wt% Ir/SC catalyst.
FIG. 3 is the HAADF-STEM characterization of the 10 wt% Ir/SC catalyst prepared in example 2 of the present invention, from which it can be seen that iridium metal is atomically dispersed on the SC support and no iridium particles are found.
FIG. 4 is an EXAFS characterization of a 10 wt% Ir/SC catalyst prepared in example 2 of the present invention, from which it can be seen that iridium exists mainly in the form of Ir-S coordination, and no Ir-Ir bond is found.
Example 3
The synthesis procedure for the SC support is the same as in example 1, steps a-c;
b. placing the obtained 95mg SC carrier and rhodium chloride solution containing 5mg rhodium in a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 200-300 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-3 h; naturally cooling to room temperature to obtain the atom dispersed 5 wt% Rh/SC catalyst.
FIG. 5 is the HAADF-STEM characterization of a 5 wt% Rh/SC catalyst prepared in example 3 of the invention, from which it can be seen that rhodium metal is atomically dispersed on the SC support and no rhodium particles are found.
FIG. 6 is an EXAFS characterization of the 5 wt% Rh/SC catalyst prepared in example 3 of the present invention, from which it can be seen that rhodium exists mainly in the form of Rh-S coordination, and no Rh-Rh bond is found.
Example 4
Synthesis of SC support the procedure was the same as the a-c procedure in example 1
b. Placing the obtained 95mg SC carrier and ruthenium chloride solution containing 5mg ruthenium in a 100mL round-bottom flask, and adding water for dilution (the total volume is kept at 50mL) to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain the catalyst-1.
c. The obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 200-300 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-3 h; naturally cooling to room temperature to obtain the 5 wt% Ru/SC catalyst with dispersed atoms.
FIG. 7 is a HAADF-STEM characterization of a 5 wt% Ru/SC catalyst prepared in example 4 of the invention, from which it can be seen that Ir metal is atomically dispersed on the SC support and no metallic iridium particles are found.
FIG. 8 is an EXAFS characterization of a 5 wt% Ru/SC catalyst prepared according to example 4 of the present invention, from which it can be seen that iridium exists predominantly in the Ru-S coordinated form, with no Ru-Ru bonds being found.
Example 5
The synthesis procedure for the SC support is the same as in example 1, steps a-c.
b. Placing the obtained 95mg SC carrier and chloropalladate solution containing 5mg palladium in a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 200-400 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-3 h; naturally cooling to room temperature to obtain the atom dispersed 5 wt% Pd/SC catalyst;
FIG. 9 is a HAADF-STEM characterization of a 5 wt% Pd/SC catalyst prepared in example 5 of the present invention, from which it can be seen that palladium metal is atomically dispersed on the SC support and no palladium particles are found.
FIG. 10 is an EXAFS characterization of a 5 wt% Pd/SC catalyst prepared in example 5 of the present invention, from which it can be seen that palladium exists mainly in the form of Pd-S coordination, and no Pd-Pd bond is found.
Example 6
The synthesis procedure for the SC support is the same as in example 1, steps a-c.
b. Placing the obtained 95mg SC carrier and a methyl rhenium trioxide ethanol solution containing 5mg rhenium in a 100mL round-bottom flask, adding ethanol for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, introducing pure He gas, heating the tube furnace to 400-600 ℃ at the speed of 5-10 ℃/min, and keeping the temperature for 1-3 h; naturally cooling to room temperature to obtain the 5 wt% Re/SC catalyst with dispersed atoms.
Example 7
The synthesis procedure for the SC support is the same as in example 1, steps a-c;
b. putting the obtained 99mg SC carrier and chloroauric acid aqueous solution containing 1mg gold into a 100mL round-bottom flask, adding 10-20 mL aqua regia to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, and stirring until the solution is completely volatilized to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing pure 5 vol% H2Heating the tubular furnace to 150-250 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 2-5 h; naturally cooling to room temperature to obtain the atomically dispersed 1 wt% Au/SC catalyst.
Example 8
The synthesis procedure for the SC support is the same as in example 1, steps a-c;
b. placing the obtained 95mg SC carrier and ferric nitrate solution containing 5mg iron in a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 400-600 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-4 h; naturally cooling to room temperature to obtain the 5 wt% Fe/SC catalyst with dispersed atoms.
Example 9
The synthesis procedure for the SC support was the same as in examples 1 a-c;
b. placing the obtained 95mg SC and copper nitrate solution containing 5mg copper into a 100mL round-bottom flask, adding water for dilution (the total volume is kept at 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 1-2h, stirring for 12h, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 was placed in a quartz boat, and 5 vol% H was introduced2Heating the tubular furnace to 400-600 ℃ at the speed of 5-10 ℃/min by using Ar gas, and keeping the temperature for 1-4 h; naturally cooling to room temperature to obtain the 5 wt% Cu/SC catalyst with dispersed atoms.
Example 10
The Ir/SC catalyst with atomic-scale dispersion obtained in the example 2, Ir/BP2000 synthesized by Ir supported on BP2000 and commercial Ir/C catalyst are used for quinoline hydrogenation reaction in a high-pressure reaction kettle; the reaction conditions are 0.5mmol of substrate and 0.1 mol% of Ir, the reaction time is 2h, the reaction pressure is 2MPa, and the temperature is 100 ℃.
FIG. 11 is a comparison of quinoline hydrogenation activity for Ir/SC, Ir/BP2000, and commercial Ir/C, from which it can be seen that the activity of the atomically dispersed Ir catalyst is much higher than the other two catalysts.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. An atom dispersed composite material, comprising sulfur-doped mesoporous carbon and metal atoms loaded on the surface of the sulfur-doped mesoporous carbon, wherein the metal atoms form coordination bonds with sulfur in the mesoporous carbon; and the metal atoms can not be agglomerated to form a metal bond;
the preparation method of the atom dispersed composite material comprises the following steps:
mixing sulfur-doped mesoporous carbon, metal salt and a solvent, and drying to obtain an initial mixture;
carrying out heat treatment on the initial mixture to obtain an atom dispersed composite material; the temperature of the heat treatment is 150-600 ℃;
the heating rate of the heat treatment is 2-15 ℃/min.
2. The atom-dispersed composite of claim 1 wherein the metal atom loading is from 1 wt% to 10 wt%.
3. The atom-dispersed composite according to claim 1, wherein the metal atom is one selected from Fe, Co, Ni, Cu, Ru, Pd, Rh, Re, Os, Ir, Pt, and Au.
4. The atom dispersed composite of claim 1, wherein the sulfur-doped mesoporous carbon is prepared by a method comprising:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
5. The atom-dispersed composite of claim 4 wherein the sulfur-containing small organic molecule is 2, 2' -bithiophene and the transition metal salt is selected from the group consisting of cobalt nitrate hexahydrate; the sulfur-containing organic micromolecules and SiO2The mass ratio of the small balls to the transition metal salt is 2:2: 1; the calcining temperature is 600-900 ℃.
6. The atom-dispersed composite material according to claim 1, wherein the heat treatment is performed in an atmosphere of argon, helium, or a hydrogen gas mixture; the hydrogen gas mixture is selected from a mixture of hydrogen and helium or a mixture of hydrogen and argon; the gas flow rate of the atmosphere is 50-500 mL/min.
7. Use of the atom dispersed composite of any one of claims 1 to 6 in hydrocatalysis.
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