Metal cluster internal modification organic cage material, preparation method and application thereof
The one-pot method of solvent-thermal synthesis of the organic cage material in the Ag4Cl4 cubic alkane cluster was solved, and the problem of failure to systematically explore the precise domain limit of metal clusters and the dynamic response characteristics of the organic cage in the prior art was solved, and the catalytic effect of efficient CO2 reduction was achieved.
Patent Information
- Application Number
- CN202510398668.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-01
- Publication Date
- 2025-08-08
AI Technical Summary
In the prior art, artificially constructed enzyme-like catalysts mainly focus on the coordination cages of single metal nodes, and failed to systematically explore a composite system that combines the precise domain of metal clusters and the dynamic response characteristics of organic cages.
The one-pot method is used to synthesize the atomically accurate Ag4Cl4 cubic cube cluster-modified organic cage material with atomic level. The metal cluster-modified organic cage material is prepared by imine condensation. The molecular structure is composed of the peripheral tetrahedral organic cage and the core Ag4Cl4 cubic cubes, and chloride ions and silver ions occupy the vertices of the cubic cubes symmetrically.
High CO2 reduction selectivity and Faraday efficiency were achieved, and the catalyst achieved a 92.76% CO Faraday efficiency at -1.15 V vs RHE voltage, with a smaller charge transfer resistance and a lower overpotential.
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Figure CN120441854A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of organic molecular cages, and in particular relates to a metal cluster internally modified organic cage material, a preparation method and an application thereof. Background Art
[0002] Porous organic cages are a new class of crystalline porous materials formed by self-assembly of discrete molecular units through dynamic covalent bonds (such as imine and boronate bonds). Their customizable, permanent cavity structure and excellent solvent dispersibility make them ideal supports for the design of enzyme-like catalysts. Since the 1980s, metal ions have been recognized as effective templates for the formation of organic cage molecules. The templating effect of metal ions or clusters appears to enable the directed assembly and diversification of organic cages.
[0003] While most research focuses on metal nanoparticles, only Bartosz Szyszko's group has achieved the self-assembly of silver clusters into pyrrole cages by studying the size and alkalinity of anions. Confining atomically precise metal clusters within the cavities of organic cages not only improves the cluster's stability but also enables the directed assembly of organic cages, mimicking the "metal-organic synergistic" catalytic mechanism of natural enzymes.
[0004] However, artificially constructed enzyme-like catalysts still mainly focus on the coordination cages of single metal nodes, while the composite system that combines the precise confinement of metal clusters with the dynamic response characteristics of organic cages has not been systematically explored. Summary of the Invention
[0005] The present application proposes to provide a metal cluster modified organic cage material, preparation method and application thereof, which are simple to operate and have a short cycle. The material can be tested by X-ray single crystal diffractometer to obtain its definite molecular formula and molecular structure. It is used to catalyze CO2 reduction and has a small charge transfer resistance, high selectivity and low overpotential. It can achieve a CO2 Faradaic efficiency of 92.76% at a voltage of -1.15 V vs RHE under the condition of potassium chloride as the electrolyte.
[0006] To this end, the first aspect of the present application provides a metal cluster modified organic cage material, the technical solution adopted is as follows: a metal cluster modified organic cage material, Its chemical formula is: C 108 H 108 Ag4Cl4N 12 P4; The space group produced by its crystallization is: It crystallizes in the triclinic system with space group P-1 and unit cell parameters: a = 5.4792(14)Å, b = 17.5351(15)Å, c = 22.867(2)Å, α = 88.240(3)°, β = 72.095(3)°, γ = 65.381(3)°, V = 5335.3Å 3 ; Among them, a, b, and c represent the axis lengths of the three groups of unit cells respectively. ， α 、 β and γ represent the axis angles of the unit cell, respectively ， V represents the volume of each unit cell.
[0007] In a second aspect, the present application provides a method for preparing the above-mentioned metal cluster-modified organic cage material, which comprises the following steps: S1. dissolving benzaldehyde, silver chloride, and a chain amine in a mixed solvent and stirring to obtain a mixture A; S2. Transfer the mixture A described in S1 into the polytetrafluoroethylene liner of a stainless steel autoclave and fasten the cover; S3. After tightening the stainless steel autoclave in S2, transfer it to an electric blast drying oven and keep it at 80-100 degrees Celsius for 20-30 hours. Then naturally cool it to room temperature and remove the colorless block crystals that appear in the polytetrafluoroethylene liner; S4. Wash the block crystals obtained in S3 with acetonitrile and dry them at room temperature to obtain the organic cage material.
[0008] Preferably, the mass ratio of benzaldehyde, silver chloride and chain amine in S1 is 2:1:2.
[0009] Preferably, the mixed solvent in S1 is a nitrogen-containing solvent, an alcohol and a third solvent, and the mass ratio of the three is 1:2:2 to 1:4:4.
[0010] Preferably, the benzaldehyde in S1 includes at least one of 2-bis(diphenylphosphino)benzaldehyde, 2,2',2''-phosphonotribenzaldehyde, 2-[bis(3,5-dimethylphenyl)phosphino]benzaldehyde, 4-(diphenylphosphino)benzaldehyde, 2,2'-(phenylphosphinodiyl)dibenzaldehyde, and 4,4',4''-phosphinotriyltribenzaldehyde.
[0011] Preferably, the chain amine in S1 includes at least one of propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, and cystamine.
[0012] Preferably, the nitrogen-containing solvent in S1 is N,N-dimethylformamide, N,N-diethylformamide or N,N-dimethylacetamide.
[0013] Preferably, the alcohol is methanol, ethanol, n-butanol, isopropanol, or n-propanol; and the third solvent is acetonitrile, tetrahydrofuran, or 1,4-dioxane.
[0014] Preferably, the total mass of benzaldehyde, silver chloride and chain amine in S1 is 50 mg to 100 mg, and the total volume of the mixed solvent used is 2 ml to 6 ml.
[0015] In a third aspect, the present application provides an application of the above-mentioned metal cluster modified organic cage material for electrochemical reduction of CO2 reaction.
[0016] The working principle and beneficial effects of this application are: 1. The present invention adopts a simple one-pot solvent thermal method to directly synthesize atomically precise Ag4C l4 The modification of organic cage materials within cubane clusters is simple to operate and has a short cycle.
[0017] 2. The catalyst material obtained in the present invention is a crystalline material, which can be tested by an X-ray single crystal diffractometer to obtain its definite molecular formula and molecular structure.
[0018] 3. This invention utilizes metal clusters protected by organic cages to design catalysts, a feat unprecedented in the art. The AgCl cubane-clustered modified organic cage material described herein is obtained through imine condensation. Its molecular structure consists of a tetrahedral organic cage surrounding it and an AgCl cubane core, with chloride ions and silver ions symmetrically occupying the vertices of the cubane. Furthermore, because the bond length of one edge of the cubane is longer than that of a normal silver-chloride bond, the cubane within the organic cage has an open structure.
[0019] 4. The catalyst obtained by the present invention is used for catalytic CO2 reduction, and has a small charge transfer resistance, high selectivity, and low overpotential, so that it can achieve a CO2 Faradaic efficiency of 92.76% at a voltage of -1.15 V vs RHE under the condition of potassium chloride as the electrolyte. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The present application will be further described in detail below with reference to the accompanying drawings and specific implementation methods.
[0021] Figure 1 The ball-and-stick model diagram of the molecular structure determined by single crystal diffraction experiments of the present invention; Figure 2 This is a comparison diagram of the current density of the linear sweep voltammetry test under CO2 / Ar atmosphere of the present invention; Figure 3 The products of electrocatalytic CO2 reduction at different potentials and their Faraday efficiency diagrams of the present invention; Figure 4The X-ray powder diffraction patterns of the present invention before and after the electrocatalytic CO2 reduction reaction; Figure 5 This is a Fourier transform infrared spectrum diagram of the present invention before and after the electrocatalytic CO2 reduction reaction. DETAILED DESCRIPTION
[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.
[0023] To this end, the first aspect of this embodiment provides a metal cluster modified organic cage material, the technical solution adopted is as follows: a metal cluster modified organic cage material, Its chemical formula is: C 108 H 108 Ag4Cl4N 12 P4; The space group produced by its crystallization is: It crystallizes in the triclinic system with space group P-1 and unit cell parameters: a = 5.4792(14)Å, b = 17.5351(15)Å, c = 22.867(2)Å, α = 88.240(3)°, β = 72.095(3)°, γ = 65.381(3)°, V = 5335.3Å 3 ; Among them, a, b, and c represent the axis lengths of the three groups of unit cells respectively. ， α 、 β and γ represent the axis angles of the unit cell, respectively. ， V represents the volume of each unit cell.
[0024] In a second aspect, the present application provides a method for preparing the above-mentioned metal cluster-modified organic cage material, which comprises the following steps: S1, dissolving benzaldehyde, silver chloride and chain amine in a mixed solvent and stirring to obtain a mixture A; S2. Transfer the mixture A described in S1 into the polytetrafluoroethylene liner of a stainless steel autoclave and fasten the cover; S3. After tightening the stainless steel autoclave in S2, transfer it to an electric blast drying oven and keep it at 80-100 degrees Celsius for 20-30 hours. Then naturally cool it to room temperature and remove the colorless block crystals that appear in the polytetrafluoroethylene liner; S4. Washing the block crystals obtained in S3 with acetonitrile and drying at room temperature to obtain the organic cage material.
[0025] The mass ratio of benzaldehyde, silver chloride and chain amine in S1 is 2:1:2.
[0026] The mixed solvent in S1 is a nitrogen-containing solvent, an alcohol and a third solvent, and the mass ratio of the three is 1:2:2 to 1:4:4.
[0027] Among them, the benzaldehyde in S1 includes at least one of 2-bis(diphenylphosphino)benzaldehyde, 2,2',2''-phosphonotribenzaldehyde, 2-[bis(3,5-dimethylphenyl)phosphino]benzaldehyde, 4-(diphenylphosphino)benzaldehyde, 2,2'-(phenylphosphinodiyl)dibenzaldehyde, and 4,4',4''-phosphinotriyltribenzaldehyde.
[0028] The chain amine in S1 includes at least one of propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, and cystamine.
[0029] The nitrogen-containing solvent in S1 is N,N-dimethylformamide, N,N-diethylformamide or N,N-dimethylacetamide.
[0030] Wherein, the alcohol is methanol, ethanol, n-butanol, isopropanol or n-propanol; and the third solvent is acetonitrile, tetrahydrofuran or 1,4-dioxane.
[0031] The total mass of benzaldehyde, silver chloride and chain amine in S1 is 50 mg to 100 mg, and the total volume of the mixed solvent used is 2 ml to 6 ml.
[0032] In a third aspect, the present application provides an application of the above-mentioned metal cluster modified organic cage material for electrochemical reduction of CO2 reaction.
[0033] The specific embodiments of this application are as follows: Example 1: 10 mg of 2,2',2''-phosphonotritylaldehyde, 10 mg of silver chloride, and 20 μL of dibutylene glycol were dissolved in a mixed solvent of 0.5 mL of N,N-dimethylformamide, 0.5 mL of ethanol, and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to the Teflon-lined interior of a stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 90°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, block-shaped crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0034] Example 2: 10 mg of 4,4',4''-phosphine triphenyl tribenzaldehyde, 10 mg of silver chloride, and 20 μL of dibutyl diamine were dissolved in a mixed solvent of 0.5 mL of N,N-dimethylformamide, 0.5 mL of ethanol, and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to a Teflon-lined stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 90°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, block-shaped crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0035] Example 3: Dissolve 10 mg of 2,2',2''-phosphonotriadialdehyde, 10 mg of silver chloride, and 20 μL of diaminodiphenylamine in 5 mM acetonitrile and stir thoroughly. The mixture is then transferred to a Teflon-lined stainless steel autoclave and the lid is secured. The autoclave is then tightened and transferred to an electric forced-air drying oven. After maintaining the temperature at 90°C for one day, the temperature is allowed to cool naturally to room temperature, resulting in the formation of a large number of colorless, block-shaped crystals. The resulting flaky crystals are then washed with acetonitrile and dried at room temperature to yield the organic cage material.
[0036] Example 4: 10 mg of 2-[bis(3,5-dimethylphenyl)phosphino]benzaldehyde, 10 mg of silver chloride, and 20 μL of pentamethylenediamine were dissolved in a mixed solvent of 0.5 mL of N,N-dimethylformamide, 0.5 mL of ethanol, and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to the Teflon-lined interior of a stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 90°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, square crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0037] Example 5: 10 mg of 2,2',2''-phosphonotritylaldehyde, 10 mg of silver chloride, and 20 μL of hexamethylenediamine were dissolved in a mixed solvent of 0.5 mL of N,N-dimethylformamide, 0.5 mL of ethanol, and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to a Teflon-lined stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 100°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, block-shaped crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0038] Example 6: 10 mg of 4,4',4''-phosphine triphenyl tribenzaldehyde, 10 mg of silver chloride, and 20 μL of propylene diamine were dissolved in a mixed solvent of 0.5 mL of N,N-dimethylacetamide, 0.5 mL of ethanol, and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to a Teflon-lined stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 90°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, square crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0039] Example 7: 10 mg of 4,4',4''-phosphine triphenyl tribenzaldehyde, 10 mg of silver chloride, and 20 μL of hexamethylenediamine were dissolved in a mixed solvent of 1 mL of N,N-dimethylacetamide and 1 mL of acetonitrile and stirred thoroughly. The mixture was then transferred to a Teflon-lined stainless steel autoclave and the lid was secured. The autoclave was tightened and transferred to an electric forced-air drying oven. After being maintained at 90°C for one day, the temperature was naturally cooled to room temperature, resulting in the formation of a large number of colorless, square crystals. The resulting flaky crystals were washed with acetonitrile and dried at room temperature to obtain the organic cage material.
[0040] Example 8: Dissolve 10 mg of 2,2'-(phenylphosphinodiyl)benzaldehyde, 10 mg of silver chloride, and 20 μL of butanediamine in a mixture of 1 mL of N,N-dimethylacetamide and 1 mL of methanol and stir thoroughly. The mixture is then transferred to a Teflon-lined stainless steel autoclave and the lid is secured. The autoclave is then tightened and transferred to an electric forced-air drying oven. After maintaining it at 90°C for one day, the temperature is allowed to cool naturally to room temperature, resulting in the formation of a large number of colorless, blocky crystals. The resulting flaky crystals are then washed with acetonitrile and dried at room temperature to yield the organic cage material.
[0041] The present invention is simple to operate and can prepare atomically precise functionalized Ag4Cl4 cluster-modified imine-based organic cage materials through a one-pot solvothermal method. Figure 1 As shown, the molecular structure of the organic cage material consists of an Ag4Cl4 cubane core and an outer tetrahedral organic cage. The outer tetrahedral organic cage exhibits adaptive properties, twisting and rotating itself to adapt to the size of the Ag4Cl4 core.
[0042] The CO2RR activity of the organic cage catalyst material of this embodiment was evaluated in a CO2-saturated 1 M KCl (pH = 4.2) solution. Figure 2 As shown, the current density response in a carbon dioxide saturated atmosphere is higher than that in an argon saturated atmosphere, indicating that the organic cage catalyst has catalytic activity for CO2 reduction.
[0043] The organic cage catalyst material of this embodiment, when using potassium chloride as the electrolyte, produces a volcanic-shaped distribution of the reduction product CO at a potential of -0.95 to -1.25 V vs RHE. At a voltage of -1.15 V vs RHE, a CO Faradaic efficiency of 92.76% can be achieved. Figure 3 shown.
[0044] The organic cage catalyst material of this embodiment can still remain stable after catalysis, as shown by the X-ray powder diffraction pattern and Fourier transform infrared spectrum, which proves that it has good stability. Figure 4 , Figure 5 shown.
[0045] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A metal cluster modified organic cage material, characterized by: Its chemical formula is: C 108 H 108 Ag4Cl4N 12 P4; The space group produced by its crystallization is: It crystallizes in the triclinic system with space group P-1. The unit cell parameters are: a = 5.4792(14)Å, b = 17.5351(15)Å, c = 22.867(2)Å, α = 88.240(3)°, β = 72.095(3)°, γ = 65.381(3)°, V = 5335.3Å. 3 ; Among them, a, b, and c represent the axis lengths of the three groups of unit cells respectively. ， α 、 β and γ represent the axis angles of the unit cell, respectively. ， V represents the volume of each unit cell.
2. The method for preparing the metal cluster modified organic cage material according to claim 1, characterized in that , including the following steps: S1. dissolving benzaldehyde, silver chloride, and a chain amine in a mixed solvent and stirring to obtain a mixture A; S2. Transfer the mixture A described in S1 into the polytetrafluoroethylene liner of a stainless steel autoclave and fasten the cover; S3. After tightening the stainless steel autoclave in S2, transfer it to an electric blast drying oven and keep it at 80-100 degrees Celsius for 20-30 hours. Then naturally cool it to room temperature and remove the colorless block crystals that appear in the polytetrafluoroethylene liner; S4. Wash the block crystals obtained in S3 with acetonitrile and dry them at room temperature to obtain the organic cage material.
3. The method for preparing the metal cluster modified organic cage material according to claim 2, characterized in that , the mass ratio of benzaldehyde, silver chloride and chain amine in S1 is 2:1:
2.
4. The method for preparing the metal cluster modified organic cage material according to claim 2, characterized in that The mixed solvent in S1 is a nitrogen-containing solvent, an alcohol and a third solvent, and the mass ratio of the three is 1:2:2 to 1:4:
4.
5. The method for preparing the metal cluster modified organic cage material according to claim 2, characterized in that The benzaldehyde in S1 includes at least one of 2-bis(diphenylphosphino)benzaldehyde, 2,2',2''-phosphonotribenzaldehyde, 2-[bis(3,5-dimethylphenyl)phosphino]benzaldehyde, 4-(diphenylphosphino)benzaldehyde, 2,2'-(phenylphosphinodiyl)dibenzaldehyde, and 4,4',4''-phosphinotriyltribenzaldehyde.
6. The method for preparing the metal cluster modified organic cage material according to claim 2, characterized in that The chain amine in S1 includes at least one of propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, and cystamine.
7. The method for modifying organic cage materials within metal clusters according to claim 4, characterized in that , the nitrogen-containing solvent in S1 is N,N-dimethylformamide or N,N-diethylformamide or N,N-dimethylacetamide.
8. The method for preparing the metal cluster modified organic cage material according to claim 4, characterized in that , the alcohol is methanol or ethanol or n-butanol or isopropanol or n-propanol; the third solvent is acetonitrile or tetrahydrofuran or 1,4-dioxane.
9. The method for preparing the metal cluster modified organic cage material according to claim 2, characterized in that , the total mass of benzaldehyde, silver chloride and chain amine in S1 is 50 mg to 100 mg, and the total volume of the mixed solvent used is 2 ml to 6 ml.
10. The use of the metal cluster modified organic cage material as claimed in claim 1, characterized in that: Used for electrochemical reduction of CO2 reaction.