CN110801863B - Cyclodextrin-based transition metal monoatomic catalytic material and preparation method thereof - Google Patents
Cyclodextrin-based transition metal monoatomic catalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a cyclodextrin-based transition metal single-atom catalytic material, which comprises the following steps: providing a cyclodextrin cross-linked polymer and a transition metal precursor; clathrating the transition metal precursor with a cyclodextrin cross-linked polymer to obtain a clathrate; and reducing the inclusion compound by using a reducing agent, and treating to obtain the cyclodextrin-based transition metal monatomic catalytic material. The invention further provides a cyclodextrin-based transition metal single-atom catalytic material.
Description
Technical Field
The invention relates to a cyclodextrin-based transition metal single-atom catalytic material and a preparation method thereof.
Background
The supported metal catalyst is widely used in industrial fields such as environment, energy, medicine and the like as a typical heterogeneous catalyst. However, for a supported catalyst, only surface metal atoms are catalytic active sites, and internal metal atoms are not utilized, so that the cost of the catalyst is greatly increased due to the low atom utilization efficiency because precious metals are expensive and scarce. In recent years, monatomic catalytic materials have been developed, in which active components are highly dispersed on an atomic level, and metal atoms are used at 100% to exhibit excellent catalytic performance. The brand new catalytic material has become a necessary trend for the future catalytic chemical development. However, there are still few reports on such a single-atom catalytic material and a method for preparing the same, due to limitations of preparation processes and materials themselves.
Disclosure of Invention
In view of the above, it is necessary to provide a single-atom catalytic material and a preparation method thereof, where the cyclodextrin-based transition metal single-atom catalytic material is a new single-atom catalytic material, and the preparation method thereof has wide versatility and can reduce the preparation cost of single-atom catalysts with different metal elements.
A preparation method of a cyclodextrin-based transition metal single-atom catalytic material comprises the following steps:
s1, providing a cyclodextrin cross-linked polymer and a transition metal precursor;
s2: using the cyclodextrin cross-linked polymer to include the transition metal precursor to obtain a inclusion compound;
s3: and reducing the inclusion compound by using a reducing agent, and treating to obtain the cyclodextrin-based transition metal monatomic catalytic material.
A cyclodextrin-based transition metal monoatomic catalytic material includes a cyclodextrin cross-linked polymer carrier and a plurality of transition metal atoms anchored to the cyclodextrin cross-linked polymer carrier as individual atoms.
The preparation method of the cyclodextrin-based transition metal single-atom catalytic material provided by the invention utilizes cyclodextrin cross-linked polymers commonly used in supermolecule chemistry, selects a transition metal precursor with a proper molecular size to form an inclusion compound with the cyclodextrin macrocycle cavity, and further reduces the inclusion compound to obtain the cyclodextrin-based transition metal single-atom catalytic material. The preparation method has wide universality, can reduce the preparation cost of the monatomic catalyst with different metal elements, can be applied to the fields of energy, catalysis, medicines, biology and the like, and has extremely wide market prospect. When the cyclodextrin-based transition metal single-atom catalytic material obtained by the preparation method is used as a supported metal catalyst, the transition metal atoms are anchored on a cyclodextrin cross-linked polymer carrier in a single-atom form, the transition metal is fully utilized, good catalytic performance can be realized only by using a small amount of transition metal, and the cost of the supported metal catalyst is greatly reduced.
Drawings
FIG. 1 is an electron micrograph of a cyclodextrin-based transition metal single-atom catalytic material provided in example 1 of the present invention.
FIG. 2 is an electron micrograph of a cyclodextrin-based transition metal single-atom catalytic material provided in example 2 of the present invention.
FIG. 3 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material provided in example 3 of the present invention.
FIG. 4 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material provided in example 4 of the present invention.
FIG. 5 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material provided in example 5 of the present invention.
FIG. 6 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material according to example 6 of the present invention.
FIG. 7 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material according to example 7 of the present invention.
FIG. 8 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material according to example 8 of the present invention.
FIG. 9 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material according to example 9 of the present invention.
FIG. 10 is an SEM image of a cyclodextrin-based transition metal monoatomic catalytic material according to example 10 of the present invention.
Detailed Description
The preparation method of the cyclodextrin-based transition metal single-atom catalytic material provided by the invention will be further described in detail with reference to the accompanying drawings and specific examples.
The embodiment of the invention provides a preparation method of a cyclodextrin-based transition metal single-atom catalytic material, which comprises the following steps:
s1, providing a cyclodextrin cross-linked polymer and a transition metal precursor;
s2: using the cyclodextrin cross-linked polymer to include the transition metal precursor to obtain a inclusion compound;
s3: and reducing the inclusion compound by using a reducing agent, and treating to obtain the cyclodextrin-based transition metal monatomic catalytic material.
In step S1, the cyclodextrin cross-linked polymer is a cross-linked polymer having a high degree of cross-linking and being insoluble in water. The cyclodextrin cross-linked polymer comprises one or more macrocyclic structures of different sizes, such as alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and the like. The transition metal precursor includes all transition metal salts or transition metal complexes in the subgroup of the periodic table. Specifically, the transition metal may include cobalt, nickel, copper, platinum, ruthenium, rhodium, iridium, and the like. The transition metal salt may be a carbonate, sulfate, nitrate or chloride salt. The transition metal complex may be a complex of a common organic ligand and the transition metal, such as platinum acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, iridium acetylacetonate, ruthenium dichloride (cyclooctyl-1,5-diene), iridium dicarbonyl acetylacetonate, and the like. Preferably, the molecular size of the transition metal precursor should correspond to the size of the macrocyclic cavity in the cyclodextrin cross-linked polymer, so that the cyclodextrin cross-linked polymer better contains the transition metal precursor. When the transition metal is platinum, the transition metal precursor is preferably platinum acetylacetonate. In step S1, the amounts of the cyclodextrin cross-linked polymer and the transition metal precursor are provided in terms of the mass percentage of the metal in the final cyclodextrin-based transition metal monatomic catalytic material (0.01 to 20%).
In step S2, the method of including the transition metal precursor with the cyclodextrin cross-linked polymer may be inclusion by wet stirring in a solvent or inclusion by dry grinding. The inclusion time is 1-100 h, and the inclusion temperature is 0-120 ℃.
When the cyclodextrin cross-linked polymer and the transition metal precursor are mixed by wet stirring in a solvent, the cyclodextrin cross-linked polymer and the transition metal precursor are added into the solvent together and fully stirred in the solvent for inclusion. The solvent comprises polar solvents such as water and ethanol. The resulting clathrate is dispersed in the solvent.
When dry milling is used for mixing, the cyclodextrin cross-linked polymer and the transition metal precursor are fully milled. Specifically, the grinding can be performed by ball milling, jet milling, hand milling, and other techniques.
In step S3, when the inclusion is performed in step S2 by wet stirring in a solvent to obtain a dispersion of the inclusion compound in the solvent, the steps including washing and drying may be further included. The detergent can adopt deionized water or ethanol. The drying may be vacuum drying or direct drying in the atmosphere. It will be appreciated that the washing and drying step is an optional step.
In step S3, the reducing agent includes compounds having reducing properties such as sodium borohydride, hydrogen, methanol, formaldehyde, and the like, and the reducing method includes a liquid-phase reduction method and a gas-phase reduction method. The reduction temperature is not limited, and can be selected according to actual needs, and preferably, the reduction temperature is 0-300 ℃. The reduction reaction time is not limited and can be selected according to actual needs, and preferably, the reduction reaction time can be 10 minutes to 24 hours. And after full reaction, filtering the precipitate, washing and drying the precipitate to obtain the cyclodextrin-based transition metal monoatomic catalytic material.
In step S3, when the liquid phase reduction method is employed. When the clathrate compound obtained by wet inclusion in the solvent is dispersed in the solvent in step S2, the reducing agent in liquid phase can be directly added into the solvent containing the clathrate compound, and the mixture is sufficiently stirred to perform the reduction reaction. In another embodiment, when dry-clathration is employed in step S2 to obtain a powdery clathrate, in order to more uniformly react the clathrate with the reducing agent, the powdery clathrate may be uniformly dispersed in a dispersing agent to obtain a dispersion, and then the reducing agent in liquid phase may be added to the dispersion, and sufficiently stirred to perform the reduction reaction.
In step S3, when the gas phase reduction method is adopted, the inclusion compound needs to react in the form of powder. Namely, the clathrate compound powder is put into a reaction chamber, and a gaseous reducing agent is introduced into the reaction chamber, so that the clathrate compound powder is subjected to sufficient reduction reaction in a reducing atmosphere. The reaction time can be 10 minutes to 24 hours, and the reaction temperature is 0-300 ℃. When step S2 adopts wet inclusion in a solvent to obtain an inclusion compound, the inclusion compound needs to be washed and dried to obtain inclusion compound powder, and then the inclusion compound powder is reduced by adopting a gas phase reduction method. In other embodiments, when the step S2 is performed by dry inclusion to obtain a powdery inclusion compound, the powdery inclusion compound is directly reduced by a gas phase reduction method without washing and drying.
And after the step S3, obtaining the cyclodextrin-based transition metal single-atom catalytic material. The cyclodextrin-based transition metal single-atom catalytic material is in a solid powder state. In the cyclodextrin-based transition metal single-atom catalytic material, the mass percentage of the transition metal is 0.01-20%.
The embodiment of the invention further provides a cyclodextrin-based transition metal single-atom catalytic material, which comprises a cyclodextrin cross-linked polymer carrier and a transition metal. The transition metal may be one transition metal, or two or more transition metals. The transition metal comprises a plurality of individual transition metal atoms uniformly anchored to the cyclodextrin cross-linked polymer carrier in a single atomic form. The transition metal may further include transition metal nanoparticles or/and transition metal atom clusters. Wherein the content of the plurality of single transition metal atoms in the transition metal is 50% or more. In certain embodiments, the transition metals in the cyclodextrin-based transition metal monatomic catalytic material are all present as a single atom, i.e., the cyclodextrin-based transition metal monatomic catalytic material includes only the cyclodextrin cross-linked polymer support and a single transition metal atom. From the spherical aberration electron micrographs of the cyclodextrin-based transition metal single-atom catalytic material provided in fig. 1 to 10, it can be clearly observed that the single transition metal atom is uniformly dispersed on the cyclodextrin cross-linked polymer carrier. The cyclodextrin cross-linked polymer comprises one or more macrocyclic structures of different sizes, such as alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and the like. The transition metal precursor includes all transition metal salts and transition metal complexes in the subgroup of the periodic table. Specifically, the transition metal may include cobalt, nickel, copper, platinum, ruthenium, rhodium, iridium, and the like. The mass percentage of the transition metal in the cyclodextrin based transition metal single atom catalytic material is 0.01-20%.
Hereinafter, the preparation method of the cyclodextrin-based transition metal monatomic catalytic material according to the present invention will be described in detail with reference to specific examples.
Example 1
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer, 0.021g of platinum acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin-based platinum single-atom catalytic material is prepared. The cyclodextrin-based platinum single-atom catalytic material prepared in the example is shown in FIG. 1. As can be seen from fig. 1, the metallic platinum is present in the catalytic material in the form of a single atom.
Example 2
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer, 0.021g of platinum acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, filtering, washing and drying, and introducing hydrogen at 150 ℃ for reduction to prepare the cyclodextrin-based platinum monatomic catalytic material. The cyclodextrin-based platinum monatomic catalytic material prepared in this example is shown in fig. 2. As can be seen from fig. 2, the metallic platinum is present in the catalytic material in the form of a single atom.
Example 3
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer carrier and 0.021g of platinum acetylacetonate are mixed and then ground by a dry method to form a cyclodextrin inclusion compound; then, 130mL of water is added and stirred uniformly, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added and stirred and reduced for 10min, and the cyclodextrin-based platinum monoatomic catalytic material is prepared after filtration, washing and vacuum drying. The cyclodextrin-based platinum monatomic catalytic material prepared in this example is shown in fig. 3. As can be seen from fig. 3, the metallic platinum is present in the catalytic material in the form of a single atom.
Example 4
1g of tetrafluoroterephthalonitrile cross-linked beta-cyclodextrin polymer carrier, 0.105g of platinum acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, 80mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin-based platinum single-atom catalytic material is prepared. The cyclodextrin-based platinum monatomic catalytic material prepared in this example is shown in fig. 4. As can be seen from fig. 4, the metallic platinum is present in the catalytic material in the form of a single atom.
Example 5
1g of tetrafluoroterephthalonitrile cross-linked beta-cyclodextrin polymer carrier, 0.044g of nickel acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; adding 40mL of sodium borohydride aqueous solution with the concentration of 4g/L, stirring and reducing for 10min, filtering, washing and drying in vacuum to obtain the cyclodextrin-based nickel monoatomic catalytic material. The cyclodextrin-based nickel monatomic catalytic material prepared in this example is shown in fig. 5. As can be seen from fig. 5, metallic nickel is present in the catalytic material in the form of a single atom.
Example 6
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer carrier, 0.045g of cobalt acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin-based cobalt monoatomic catalytic material is prepared. The cyclodextrin-based cobalt monoatomic catalytic material prepared in this example is shown in fig. 6. As can be seen from fig. 6, metallic cobalt is present in the catalytic material in the form of a single atom.
Example 7
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer carrier, 0.028g of dichloro (cyclooctyl-1,5-diene) ruthenium and 130mL of water were mixed and stirred for 24h to form a cyclodextrin inclusion compound; then, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin ruthenium monoatomic catalytic material is prepared. The cyclodextrin ruthenium monoatomic catalyst material prepared in this example is shown in fig. 7. As can be seen from fig. 7, the metallic ruthenium is present in the catalytic material in the form of a single atom.
Example 8
1g of tetrafluoroterephthalonitrile crosslinked beta-cyclodextrin polymer, 0.0185g of iridium dicarbonyl acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin-based iridium single-atom catalytic material is prepared. The cyclodextrin-based iridium monatomic catalytic material prepared in this example is shown in fig. 8. As can be seen from fig. 8, the metallic iridium is present in the catalytic material in the form of a single atom.
Example 9
1g of tetrafluoroterephthalonitrile cross-linked gamma-cyclodextrin polymer, 0.021g of platinum acetylacetonate and 130mL of water are mixed and stirred for 24 hours to form a cyclodextrin inclusion compound; then, 40mL of sodium borohydride aqueous solution with the concentration of 4g/L is added, stirred and reduced for 10min, filtered, washed and dried in vacuum, and the cyclodextrin-based platinum single-atom catalytic material is prepared. The cyclodextrin-based platinum monatomic catalytic material prepared in this example is shown in fig. 9. As can be seen from fig. 9, the metallic platinum is present in the catalytic material in the form of a single atom.
Example 10
Mixing 1g of epichlorohydrin crosslinked beta-cyclodextrin polymer carrier, 0.021g of platinum acetylacetonate and 130mL of water, and stirring for 24 hours to form a cyclodextrin inclusion compound; adding 40mL of sodium borohydride aqueous solution with the concentration of 4g/L, stirring and reducing for 10min, filtering, washing and drying in vacuum to prepare the cyclodextrin platinum monoatomic catalytic material. The cyclodextrin-based platinum monatomic catalytic material prepared in this example is shown in fig. 10. As can be seen from fig. 10, the metallic platinum is present in the catalytic material in the form of a single atom.
The preparation method of the cyclodextrin-based transition metal single-atom catalytic material provided by the invention has the following advantages: firstly, a transition metal precursor with a proper molecular size is selected according to a cyclodextrin macrocycle cavity by utilizing a cross-linked cyclodextrin polymer commonly used in supramolecular chemistry to form an inclusion compound with the transition metal precursor, and the inclusion compound is further reduced to obtain the cyclodextrin-based transition metal single-atom catalytic material, so that the operation is simple and controllable. Secondly, the preparation method has wide universality, can reduce the preparation cost of the monatomic catalyst with different metal elements, can be applied to the fields of energy, catalysis, medicines, biology and the like, and has extremely wide market prospect. Thirdly, when the cyclodextrin-based transition metal single-atom catalytic material obtained by the preparation method is used as a supported metal catalyst, metal atoms are anchored on a cyclodextrin cross-linked polymer carrier in a single-atom form, the metal is fully utilized, good catalytic performance can be realized only by using a small amount of metal, and the cost of the supported metal catalyst is greatly reduced.
In addition, other modifications within the spirit of the invention will occur to those skilled in the art, and it is understood that such modifications are included within the scope of the invention as claimed.
Claims (11)
1. A preparation method of a cyclodextrin-based transition metal single-atom catalytic material comprises the following steps:
s1, providing a cyclodextrin cross-linked polymer and a transition metal precursor, wherein the transition metal precursor comprises platinum acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, dichloro (cyclooctyl-1,5-diene) ruthenium or iridium dicarbonyl acetylacetonate;
s2: wet-stirring the cyclodextrin cross-linked polymer and the transition metal precursor in water or grinding the cyclodextrin cross-linked polymer and the transition metal precursor by a dry method to obtain a clathrate;
s3: reducing the inclusion compound by using a reducing agent, wherein the reducing agent comprises sodium borohydride, hydrogen, methanol or formaldehyde, and treating to obtain the cyclodextrin-based transition metal single-atom catalytic material which comprises a cyclodextrin cross-linked polymer carrier and a transition metal, wherein the transition metal comprises a plurality of single transition metal atoms, the plurality of single transition metal atoms are dispersed on the cyclodextrin cross-linked polymer carrier in the form of single atoms, and the content of the plurality of single transition metal atoms in the transition metal is more than or equal to 50%.
2. The method of claim 1, wherein the transition metal precursor is platinum acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, dichloro (cyclooctyl-1,5-diene) ruthenium, or iridium dicarbonyl acetylacetonate.
3. The method for preparing a cyclodextrin-based transition metal monatomic catalytic material according to claim 1, wherein in step S2, an inclusion is obtained by the step of wet-stirring in water, which comprises: adding the cyclodextrin cross-linked polymer and the transition metal precursor into water, fully stirring in the water for inclusion to obtain the inclusion compound, and dispersing the inclusion compound in the water.
4. The method of preparing a cyclodextrin-based transition metal monatomic catalytic material of claim 3, wherein step S3 comprises: providing a liquid phase type reducing agent, directly adding the liquid phase reducing agent into water containing the inclusion compound, and fully stirring for reduction reaction.
5. The method of claim 3, further comprising a step of washing and drying the clathrate dispersed in water to obtain a powdery clathrate.
6. The method for preparing a cyclodextrin-based transition metal monatomic catalytic material according to claim 1, wherein in step S2, an inclusion is obtained by the dry milling, which comprises: and grinding and clathrating the cyclodextrin cross-linked polymer and the transition metal precursor, and then stirring and mixing uniformly to obtain the powdery clathrate compound.
7. The method of preparing a cyclodextrin-based transition metal monatomic catalytic material of claim 6, wherein step S3 comprises: providing a gas phase reducing agent, and carrying out reduction reaction on the powdery inclusion compound in a reducing atmosphere.
8. The method of preparing a cyclodextrin-based transition metal monatomic catalytic material of claim 6, wherein step S3 comprises: providing a dispersing agent and a liquid-phase reducing agent, dispersing the powdery inclusion compound in the dispersing agent to obtain a dispersion liquid, and adding the liquid-phase reducing agent into the dispersion liquid to mix for reduction reaction.
9. A cyclodextrin-based transition metal monoatomic catalytic material manufactured by the method according to any one of claims 1 to 8, comprising a cyclodextrin cross-linked polymer support having a cyclodextrin macrocycle structure and a transition metal including a plurality of single transition metal atoms dispersed as single atoms on the cyclodextrin cross-linked polymer support, wherein the content of the plurality of single transition metal atoms in the transition metal is 50% or more.
10. The cyclodextrin-based transition metal monatomic catalytic material of claim 9 wherein the transition metal further comprises one or both of transition metal nanoparticles or transition metal atom clusters.
11. The cyclodextrin-based transition metal monatomic catalytic material of claim 9, wherein the transition metal is present in the cyclodextrin-based transition metal monatomic catalytic material in an amount of 0.01 to 20% by mass.
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