Defective Cu (I)-based organic framework material, preparation method thereof and application of defective Cu (I)-based organic framework material in catalysis of carboxylation reaction of carbon dioxide

Abstract

The invention belongs to the technical field of functional material preparation and catalysis, and provides a defective Cu (I)-based organic framework material, a preparation method thereof and application of the defective Cu (I)-based organic framework material in catalysis of carboxylation reaction of carbon dioxide. By regulating and controlling defects of different proportions, a series of novel Cu (I)-based defective organic frameworks rich in metal and Lewis alkali multi-element active sites are constructed by adopting a one-pot method; as a catalyst, in a reaction for synthesizing an acetylenic acid compound through carboxylation of carbon dioxide and aromatic alkyne with different substituent groups, synthesis of high-selectivity catalytic acetylenic acid under a normal pressure condition is realized. The organic framework material is easy to separate, the catalytic activity is not obviously reduced after the organic framework material is recycled for five times, the organic framework material has a stable structure and excellent adsorption and catalytic conversion dual functions on carbon dioxide, the problem that a current catalytic system is poor in comprehensive performance in the aspects of catalytic activity, stability, separation and reuse and the like is solved, and the organic framework material has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of functional material preparation and catalysis technology, and relates to a defective Cu(I)-based organic framework material, its preparation method, and its application in catalyzing carbon dioxide carboxylation reaction. Background Technology

[0002] Currently, effectively controlling atmospheric CO2 levels has become a major concern for researchers. Carbon capture and utilization (CCU) technology, as an emerging solution, can capture CO2 from emission sources and convert it into valuable products. Among various CCU technologies, the coupling reaction of CO2 with terminal alkynes for the preparation of propargyl acids is a current research frontier and key area. For example, the carboxylation reaction of CO2 with aromatic alkynes synthesizes phenylpropargyl acids, in which phenylpropargyl acid, as a core organic intermediate, is a key precursor in the synthesis of heterocyclic compounds such as coumarins and flavonoids. These heterocyclic compounds play an irreplaceable role in pharmaceutical and pesticide manufacturing and are of great significance for new drug development and crop protection. Simultaneously, phenylpropargyl acid is also widely used as a modifier and intermediate in the preparation of high-performance polymer materials, bringing innovative possibilities to the field of materials science.

[0003] For the carboxylation reaction of CO2 with terminal alkynes, researchers have developed various homogeneous and heterogeneous catalytic systems. Homogeneous catalysts based on noble metal complexes (such as silver, gold, and palladium), their inorganic salts, or N-heterocyclic carbene (NHC) systems exhibit excellent activity under mild conditions. However, their inherent limitations, including difficulty in separation, poor recyclability, sensitivity to air / moisture, and environmental issues, hinder their application in large-scale industry. Therefore, efforts are being made to design heterogeneous catalysts that combine easy separation, recyclability, and high activity. Current heterogeneous catalytic systems mainly immobilize coinage metals (gold, silver, and copper) on supports such as silica, porous carbon, organic frameworks, metal-organic frameworks, or metal nanoclusters. Although these catalysts can achieve the carboxylation reaction of alkynes under mild conditions with the aid of basic additives (such as cesium carbonate and potassium carbonate) and simplify the separation process, they are often complex to prepare, have poor structural stability, and are prone to metal loss. Furthermore, developing economical non-noble metal catalysts (such as copper-based catalysts) with high activity and good stability under ambient CO2 conditions remains a key challenge. In contrast, metal-organic frameworks (MOFs) exhibit great potential as heterogeneous catalysts due to their high specific surface area, tunable pore environment, and programmable active sites. Given the inherent activating power of copper (I) for terminal alkynes, copper-based MOFs are particularly suitable for alkyne carboxylation reactions. However, this includes Cu(IN)-MOFs, Cu-MOFs, and [Cu(Fbtx)2(NO3)2]. nMost reported systems, including TpBpy-Cu-14, Cu(I)-GSH / ZIF-8, and Cu2TCPP(Cu), stabilize copper sites through weak coordination. This leads to structural instability under reaction conditions, metal leaching, and insufficient density / accessibility of active sites, thus limiting their practical applications. Furthermore, Chinese patent application CN 104117390 A proposes a method for preparing a metal-organic framework catalyst supported on silver nanoparticles. This catalyst can react CO2 with phenylacetylene to convert it into phenylpropynic acid under mild reaction conditions. However, the activity of this catalyst needs improvement, and its stability is not mentioned.

[0004] In conclusion, the development of heterogeneous catalysts that combine high stability and high catalytic activity is particularly urgent. Summary of the Invention

[0005] This invention proposes a defective Cu(I)-based organic framework material, its preparation method, and its application in catalyzing the carboxylation reaction of carbon dioxide. This defective Cu(I)-based organic framework material exhibits excellent catalytic activity in the carboxylation reaction of CO2 and aromatic alkynes. It is easily separated, and its catalytic activity does not significantly decrease after five cycles. It possesses structural stability and excellent dual functionality for both adsorption and catalytic conversion of carbon dioxide, solving the problem of poor overall performance in current catalytic systems in terms of catalytic activity, stability, and separation and reuse. It has broad application prospects.

[0006] The technical solution of this invention is implemented as follows: Technical Topic 1 This invention provides a defective Cu(I)-based organic framework material, the preparation method of which includes: S1: Add the ternary alkynyl monomer, propargylamine and copper tetrafluoroborate tetraacetonitrile to the solvent and stir to obtain a mixed solution; S2: Under inert gas protection, the mixed solution obtained in S1 is heated to 50-80℃, and triethylamine is added dropwise under stirring. The reaction is then carried out for 1-6 hours. After the reaction is completed, the temperature is lowered to room temperature and post-processed to obtain defective Cu(I)-based organic framework materials. The ternary acetylene monomer is selected from any of the substances shown in the following structural formulas: .

[0007] Preferably, the molar ratio of the total molar amount of the ternary alkynyl monomer and propargylamine in S1 to the molar amount of copper tetrafluoroborate tetraacetonitrile is 0.3:1, wherein the amount of propargylamine is 20%-40% of the total molar amount of the ternary alkynyl monomer and propargylamine.

[0008] Preferably, the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 15-25 mL.

[0009] Preferably, the amount of triethylamine in S2 is 1.0%-1.5% of the volume of the solvent in S1.

[0010] Preferably, the amount of propargylamine used in S1 is 30% of the total molar amount of the ternary alkynyl monomer and propargylamine.

[0011] Preferably, the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL.

[0012] Preferably, the amount of triethylamine in S2 is 1.3% of the volume of the solvent in S1.

[0013] The solvent is selected from any one of methanol, ethanol, acetone, tetrahydrofuran, or acetonitrile.

[0014] Preferably, the solvent is acetonitrile.

[0015] Preferably, the post-processing includes filtration, washing, and drying.

[0016] Preferably, the washing process involves sequentially washing with acetonitrile, N,N-dimethylacetamide, and water.

[0017] Preferably, the drying step includes vacuum drying at 75-85°C for 10-14 hours.

[0018] Technical Theme Two The present invention also provides a method for preparing defective Cu(I)-based organic framework materials as described in Technical Topic 1.

[0019] Technical Theme 3 The present invention also provides the application of defective Cu(I)-based organic framework materials as described in Technical Subject 1 as catalysts for the carboxylation reaction of carbon dioxide and aromatic alkynes.

[0020] Preferably, the aromatic yne is a substance represented by any of the following structural formulas: .

[0021] Preferably, the carboxylation reaction temperature is 60-90℃, the CO2 pressure is 0.1 MPa, and the reaction time is 4-8 h.

[0022] Preferably, the carboxylation reaction uses a defective Cu(I)-based organic framework material as a catalyst and cesium carbonate as an auxiliary agent, so that aromatic alkynes and carbon dioxide are successively carboxylated and neutralized to synthesize phenylpropynic acid compounds.

[0023] Preferably, in the carboxylation reaction, the amount of catalyst and aromatic yne is related as follows: calculated based on the Cu content in the defective Cu(I)-based organic framework material, wherein the molar ratio of Cu to aromatic yne is 0.05-0.1:1.

[0024] Preferably, the molar ratio of cesium carbonate to aromatic yne in the carboxylation reaction is 1.2-1.8:1.

[0025] Preferably, the ratio of solvent to aromatic yne used in the reaction is 1.5-2.5 mL: 1 mmol.

[0026] Preferably, the solvent used in the reaction is N,N-dimethylformamide.

[0027] The beneficial effects of the present invention using the above technical solution are as follows: 1. The defective Cu(I)-based organic framework material provided by the present invention has the advantages of high catalytic activity, good structural stability, easy recycling, reusability, and efficient and environmentally friendly synthesis.

[0028] 2. This invention provides a one-pot method for preparing defective Cu(I)-based organic framework materials. This preparation method is simple to operate and highly efficient.

[0029] 3. This invention provides a method for using defective Cu(I)-based organic framework materials as catalysts for the carboxylation reaction of carbon dioxide and aromatic alkynes. In the reaction of catalyzing the carboxylation reaction of carbon dioxide and aromatic alkynes to prepare phenylpropynic acid compounds, the reaction conditions are mild, the catalytic activity is high, the catalyst is easy to recover, and the recycling performance is excellent. Attached Figure Description

[0030] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0031] Figure 1 This is a schematic diagram of the preparation process of the defective Cu(I)-based organic framework material of the present invention.

[0032] Figure 2 The above are FTIR chromatograms of the materials prepared in this invention, wherein (a) TEPT monomer, TEPT-MOF, TEPB-MOF, and TEPA-MOF represent 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively; (b) PA and TEPT-dMOF- x %PA represents propyneamine and Cu(I)-based organic framework materials, respectively. x =10, 30, 50, representing the Cu(I)-based organic framework materials prepared in Comparative Example 4, Example 1, and Comparative Example 5, respectively.

[0033] Figure 3 Materials prepared for this invention 13 C-spectrum, where (a) represents TEPT-MOF of Comparative Example 1; (b) represents TEPT-dMOF-30%PA of Example 1.

[0034] Figure 4 The images show X-ray photoelectron spectroscopy (XPS) spectra of the materials prepared in this invention, where (a) is the total spectrum, (b) are the C 1s spectra of TEPT-MOF and TEPT-dMOF-30%PA, (c) are the N 1s spectra of TEPT-MOF and TEPT-dMOF-30%PA, and (d) are the Cu 2p spectra of TEPT-MOF and TEPT-dMOF-30%PA.

[0035] Figure 5 The XRD patterns of the materials prepared in this invention are shown, where (a) is Cu(I)-MOF; (b) are TEPT and TEPT-dMOF- x %PA; (c) TEPT-dMOF-30%PA simulation plot.

[0036] Figure 6 The CO2 isothermal adsorption curves of the materials prepared in this invention are shown, where (a) 298 K; (b) 273 K; and (c) CO2 adsorption capacity of TEPT-dMOF-30%PA after five cycles at 298 K.

[0037] Figure 7 The catalytic product phenylpropynic acid for the preparation of materials in this invention 1 H NMR spectroscopy.

[0038] Figure 8 The diagram shows the cyclic performance evaluation of TEPT-dMOF-30%PA as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes according to the present invention. (a) Cyclic performance diagram; (b) FTIR diagram of TEPT-dMOF-30%PA before and after cycling; (c) TGA diagram of TEPT-dMOF-30%PA before and after cycling; (d) N2 adsorption and desorption diagram of TEPT-dMOF-30%PA before and after cycling. Detailed Implementation

[0039] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. Unless otherwise specified, the experimental or testing methods involved in the embodiments of this invention are conventional methods in the prior art, and their names and / or abbreviations are conventional names in the art, clearly defined in their respective fields of application. Those skilled in the art can understand the conventional process steps based on these names and apply the corresponding equipment, implementing them under conventional conditions or conditions recommended by the manufacturer. The various instruments, equipment, raw materials, or reagents used in the embodiments of this invention are not subject to any special restrictions on their source; they are all conventional products that can be purchased through legitimate commercial channels and can be prepared according to conventional methods well known to those skilled in the art.

[0041] In the examples and comparative examples described below, 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT), 1,3,5-tris(4-ethynylphenyl)benzene (TEPB), tris(4-ethynylphenyl)amine (TEPA), propyneamine (PA), and tetra(acetonitrile)copper(I)tetrafluoroborate (Cu(MeCN)4]BF4) are all commercially available.

[0042] Example 1 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPT, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL; the total molar amount of TEPT and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 30% of the total molar amount of TEPT and propargylamine; S2: Under inert gas (nitrogen) protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 80°C for 12 hours to obtain TEPT-dMOF-30%PA.

[0043] like Figure 1This diagram illustrates the preparation process of the defective Cu(I)-based organic framework material of this invention. A three-dimensional framework is formed by a ternary alkynyl monomer and a Cu(I) salt under alkaline conditions, and defects are introduced by using propargylamine as a chain terminator, resulting in a novel Cu(I)-based defective organic framework rich in metal and Lewis base multi-active sites.

[0044] Example 2 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPT, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 15 mL; the total molar amount of TEPT and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 20% of the total molar amount of TEPT and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 80°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.0% of the volume of solvent in S1). The reaction was then stirred for 1 hour. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 85°C for 10 hours to obtain TEPT-dMOF-20%PA.

[0045] Example 3 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPT, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 25 mL; the total molar amount of TEPT and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 40% of the total molar amount of TEPT and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 50°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.5% of the volume of solvent in S1). The reaction was then stirred for 6 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 75°C for 14 hours to obtain TEPT-dMOF-40%PA.

[0046] Example 4 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPB, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL; the total molar amount of TEPB and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 30% of the total molar amount of TEPB and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was naturally cooled to room temperature. After filtration, the solid product was washed with acetonitrile, N,N-dimethylacetamide and water in sequence, and then dried under vacuum at 80°C for 12 h to obtain TEPB-dMOF-30%PA.

[0047] Example 5 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPB, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 15 mL; the total molar amount of TEPB and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 20% of the total molar amount of TEPB and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 80°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.0% of the volume of solvent in S1). The reaction was then stirred for 1 hour. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 85°C for 10 hours to obtain TEPB-dMOF-20%PA.

[0048] Example 6 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPB, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol : 25 mL; the total molar amount of TEPB and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 40% of the total molar amount of TEPB and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 50°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.5% of the volume of the solvent in S1). The reaction was then stirred for 6 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 75°C for 14 hours to obtain TEPB-dMOF-40%PA.

[0049] Example 7 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPA, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL; the total molar amount of TEPA and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 30% of the total molar amount of TEPA and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 80°C for 12 hours to obtain TEPA-dMOF-30%PA.

[0050] Example 8 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPA, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 15 mL; the total molar amount of TEPA and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 20% of the total molar amount of TEPA and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 80°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.0% of the volume of the solvent in S1). The reaction was then stirred for 1 hour. After the reaction was completed, the mixture was naturally cooled to room temperature. After filtration, the solid product was washed with acetonitrile, N,N-dimethylacetamide and water in sequence, and then dried under vacuum at 85°C for 10 hours to obtain TEPA-dMOF-20%PA.

[0051] Example 9 A method for preparing a defective Cu(I)-based organic framework material includes the following steps: S1: Add TEPA, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol : 25 mL; the total molar amount of TEPA and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 40% of the total molar amount of TEPA and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 50°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.5% of the volume of the solvent in S1). The reaction was then stirred for 6 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 75°C for 14 hours to obtain TEPA-dMOF-40%PA.

[0052] Comparative Example 1 Compared to Example 1, the only difference is that propargylamine was not added. Specifically, the steps are as follows: S1: Add TEPT and copper tetrafluoroborate tetraacetonitrile in a molar ratio of 0.3:1 to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL. S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 80°C for 12 hours to obtain TEPT-MOF.

[0053] Comparative Example 2 Compared to Example 4, the only difference is that propargylamine was not added. Specifically, the steps are as follows: S1: Add TEPB and copper tetrafluoroborate tetraacetonitrile in a molar ratio of 0.3:1 to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL. S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was naturally cooled to room temperature. After filtration, the solid product was washed with acetonitrile, N,N-dimethylacetamide and water in sequence, and then dried under vacuum at 80°C for 12 hours to obtain TEPB-MOF.

[0054] Comparative Example 3 Compared to Example 7, the only difference is that propargylamine was not added. Specifically, the steps are as follows: S1: Add TEPA and copper tetrafluoroborate tetraacetonitrile in a molar ratio of 0.3:1 to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL. S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 80°C for 12 hours to obtain TEPA-MOF.

[0055] Comparative Example 4 Compared to Example 1, the only difference is the amount of raw materials used. Specifically, the steps are as follows: S1: Add TEPT, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL; the total molar amount of TEPT and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 10% of the total molar amount of TEPT and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. After filtration, the solid product was washed sequentially with acetonitrile, N,N-dimethylacetamide and water, and then dried under vacuum at 80°C for 12 hours to obtain TEPT-dMOF-10%PA.

[0056] Comparative Example 5 Compared to Example 1, the only difference is the amount of raw materials used. Specifically, the steps are as follows: S1: Add TEPT, propargylamine, and copper tetrafluoroborate tetraacetonitrile to acetonitrile and stir to obtain a mixed solution; wherein the ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 20 mL; the total molar amount of TEPT and propargylamine is 0.3 mmol, the molar amount of copper tetrafluoroborate tetraacetonitrile is 1 mmol, and the amount of propargylamine is 50% of the total molar amount of TEPT and propargylamine; S2: Under inert gas protection, the mixed solution obtained in S1 was heated to 60°C, and triethylamine was slowly added dropwise under stirring (the amount of triethylamine was 1.3% of the volume of the solvent in S1). The reaction was then stirred for 2 hours. After the reaction was completed, the mixture was naturally cooled to room temperature. After filtration, the solid product was washed with acetonitrile, N,N-dimethylacetamide and water in sequence, and then dried under vacuum at 80°C for 12 hours to obtain TEPT-dMOF-50%PA.

[0057] Test case 1. Structural characterization like Figure 2 The figures show the FTIR spectra of the materials prepared in this invention, where (a) TEPT monomer, TEPT-MOF, TEPB-MOF, and TEPA-MOF; (b) PA and TEPT-dMOF- x %PA. (By) Figure 2 As shown in (a), 3325-3200 cm -1 and 660 cm -1 CH bending vibrations of terminal alkynes can be observed at 1720-1465 cm⁻¹. According to relevant infrared spectroscopy studies, these vibrations occur at 1720-1465 cm⁻¹. -1 The peaks appearing in the range are C=C vibration peaks on the benzene ring; in the 1435-1320 cm⁻¹ range... -1 The peak at 1415-1300 cm⁻¹ is a characteristic peak of the triazine group. -1 The peak at that location corresponds to the CN-C bond stretching vibration of the benzene ring bonded to the N atom in the TEPA material; such as Figure 2 As shown in (b), in the range of 3100-2790 cm -1 860 cm -1 The peaks at the specified locations are attributed to the methylene bridge -CH2 bond and CN bond connecting the amino group in propargylamine, respectively.

[0058] like Figure 3 The materials prepared for this invention 13 C-chromatograms, where (a) TEPT-MOF; (b) TEPT-dMOF-30%PA. For TEPT-MOF, the signal at chemical shift 168 ppm is attributed to the carbon atom in the triazine ring; chemical shifts in the range of 148-113 ppm correspond to the aromatic ring. sp2 Hybridized carbon. Furthermore, the chemical shift at 75–82 ppm clearly indicates the presence of the alkynyl group. sp The hybrid carbon exhibits a new and distinct signal peak at a chemical shift of 42-25 ppm, which is attributed to the carbon atom in the -CH2 alkyl group of propargylamine, proving that the propargylamine unit has been successfully incorporated into the catalyst.

[0059] To further determine the structures of TEPT-MOF and TEPT-dMOF-30%PA, X-ray photoelectron spectroscopy (XPS) analysis was performed on both. Figure 4 , Figure 4 The overall spectrum of (a) shows that both TEPT-MOF and TEPT-dMOF-30%PA are composed of carbon (C), nitrogen (N), oxygen (O), and copper (Cu). Figure 4 (b) shows the C 1s spectra of TEPT-MOF and TEPT-dMOF-30%PA. Figure 4 (c) Presents the N 1s spectra of TEPT-MOF and TEPT-dMOF-30%PA. The characteristic peak at 398.8 eV is that of the C=NC group in TEPT-MOF, which is also present at the same position in the spectrum of TEPT-dMOF-30%PA. Furthermore, a new C-NH bond has formed. x The bond exhibits a characteristic peak at 399.9 eV, providing strong evidence for the successful introduction of propargylamine. (For example...) Figure 4 (d) shows the Cu 2p spectra of TEPT-MOF and TEPT-dMOF-30%PA.

[0060] like Figure 5 XRD characterization was performed on TEPT-MOF, TEPB-MOF, and TEPA-MOF materials. Among them, (a) Cu(I)-MOF; (b) TEPT-MOF and TEPT-dMOF- x %PA; (c) Simulation diagram of TEPT-dMOF-30%PA, Figure (a) shows that the synthesized crystal forms of several materials are similar. Figure 5 As clearly shown in (b), the introduction of propargylamine does not change the crystal plane composition of the organic framework, but the overall crystallinity of the material decreases. Further simulation analysis of TEPT-dMOF-30%PA was performed, such as... Figure 5 (c), in 6.3 o 10.9 o 16.9 o and 25.3 oObvious diffraction peaks were observed nearby, corresponding to the (100), (110), (210), and (001) crystal planes of TEPT-MOF, respectively, which are basically consistent with the simulated peaks, further confirming the successful synthesis of TEPT-dMOF-30%PA.

[0061] 2. Adsorption performance determination The CO2 adsorption performance of Cu(I) organic framework materials was determined using a volumetric method. Pretreatment was performed before the adsorption tests, including vacuum drying at 120 °C for 12 h. The CO2 adsorption performance of the Cu(I)-MOF materials was then measured using a physical adsorption analyzer at 273 K and 298 K. The 273 K and 298 K test conditions were maintained using an ice-water mixture and a water bath, respectively.

[0062] The CO2 isotherm adsorption curves of different materials were studied using the volumetric method, and the results are as follows: Figure 6 ,like Figure 6 As shown in (c), it can be seen that the adsorption capacity of TEPT-dMOF-30%PA did not decrease significantly after cycling.

[0063] Application Example 1: Catalytic application of the carboxylation reaction of CO2 with aromatic alkynes 1. Evaluation of catalytic performance in the carboxylation reaction with phenylacetylene In a 25 mL Schlenk reaction tube, 0.5 mmol of phenylacetylene, 0.75 mmol of 1.5 equiv Cs₂CO₃, a catalyst, and 1 mL of anhydrous DMF were added sequentially. The amount of catalyst was calculated based on the Cu content in the defective Cu(I)-based organic framework materials prepared in the examples and comparative examples. The molar ratio of Cu to aromatic acetylene was 0.08:1. The specific Cu content was calculated using ICP-OES characterization. The reaction tube was sealed with a stopper and subjected to a freeze-pump-thaw cycle for gas exchange. The reaction tube was then connected to an atmospheric pressure CO₂ balloon, and the reaction mixture was stirred at 80 °C for 6 h. After the reaction was completed, it was cooled to room temperature. The catalyst was separated by filtration, and the filtrate was diluted with water (15 mL) and extracted with dichloromethane (3 × 10 mL). The aqueous phase was acidified to pH=1 with 1 M hydrochloric acid and then extracted three times with ethyl acetate (3 × 10 mL). The bound organic phase was washed with saturated NaCl solution, dried over anhydrous Na₂SO₄, and then filtered. The solvent was removed under reduced pressure to obtain the product phenylpropynic acid. 1 HNMR spectrum, such as Figure 7 As shown.

[0064] The reaction equation for the synthesis of phenylpropynic acid from phenylacetylene and CO2 is as follows: The catalytic reaction yields of different materials are shown in Table 1 below.

[0065] Table 1. Catalytic reaction yields of different materials 2. Recycling performance To evaluate the catalyst's recyclability, the TEPT-dMOF-30%PA catalyst separated by filtration in step 1 was washed three times with dichloromethane and ethyl acetate, respectively, filtered, and then vacuum-dried at 80°C for 6 h. It was then directly reused in subsequent catalytic reactions. The catalytic reaction conditions remained the same as in "1. Evaluation of Catalytic Performance in the Carboxylation Reaction with Phenylacetylene".

[0066] like Figure 8 The graph shows the cyclic performance evaluation of TEPT-dMOF-30%PA as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes. Figure 8 As shown in (a), under the same conditions, after 5 cycles of catalytic reaction, the product yield of TEPT-dMOF-30%PA still exceeded 90%, while the selectivity remained unchanged at 99%. This indicates that the catalyst has good reusability. (Comparison) Figure 8 The FTIR spectrum in (b) shows that the recovered TEPT-dMOF-30%PA exhibits characteristic absorption bands similar to those of the fresh catalyst after 5 cycles, indicating that the loss of functional groups in its structure is negligible. Based on the N2 adsorption-desorption characterization results ( Figure 8 -d), after repeated use, the BET specific surface area of ​​TEPT-dMOF-30%PA (from 372 m²) 2 / g decreased to 304 m 2 / g), after testing, the pore size distribution diagram shows that the pore volume (from 0.73cm) 3 / g decreased to 0.68 cm 3 The CO2 adsorption capacity decreased slightly. However, the pore size of BJH remained essentially unchanged, indicating that the integrity of the pore structure was not significantly damaged during the recovery process. Furthermore, the CO2 adsorption capacity of the catalyst did not decrease significantly after five cycles. In conclusion, the TEPT-dMOF-30%PA catalyst exhibits significant structural stability and recyclability.

[0067] Similarly, the catalysts of Examples 2-9 were subjected to the same recycling verification. After five cycles, the product yield was still over 80%, while the selectivity remained unchanged at 99%, and the catalyst’s adsorption capacity for CO2 did not decrease significantly.

[0068] 3. Determine the universality and the reaction results with different aromatic alkynes. In a 25 mL Schlenk tube, aromatic yne (0.5 mmol), 1.5 equiv Cs₂CO₃ (0.75 mmol), TEPT-dMOF-30%PA (0.01 g, the amount of catalyst was calculated based on the Cu content in the TEPT-dMOF-30%PA prepared in Example 1, with a Cu to aromatic yne molar ratio of 0.08:1, and the specific Cu content was calculated using ICP-OES characterization), and anhydrous DMF (1 mL) were added sequentially. The tube was sealed with a stopper and subjected to a freeze-pump-thaw cycle for gas exchange. The tube was then connected to an atmospheric pressure CO₂ balloon, and the reaction mixture was stirred at 80 °C for 6 h. After the reaction was complete, the mixture was cooled to room temperature. The catalyst was separated by filtration, and the filtrate was diluted with water (15 mL) and extracted with dichloromethane (3 × 10 mL). The aqueous phase was acidified to pH=1 with 1 M hydrochloric acid and then extracted three times with ethyl acetate (3 × 10 mL). The combined organic phase was washed with saturated NaCl solution, dried over anhydrous Na₂SO₄, and filtered. The solvent was removed under reduced pressure to obtain the product.

[0069] The substrate range of CO2 carboxylation reaction was studied using the TEPT-dMOF-30%PA / Cs2CO3 system as a catalyst. As shown in Table 2, the substrate range study under the synergistic catalysis of the TEPT-dMOF-30%PA / Cs2CO3 system shows that the TEPT-dMOF-30%PA / Cs2CO3 catalytic system has good versatility.

[0070] Table 2 The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A defective Cu(I)-based organic framework material, characterized in that, Preparation methods include: S1: Add the ternary alkynyl monomer, propargylamine and copper tetrafluoroborate tetraacetonitrile to the solvent and stir to obtain a mixed solution; S2: Under inert gas protection, the mixed solution obtained in S1 is heated to 50-80℃, and triethylamine is added dropwise under stirring. The reaction is then carried out for 1-6 hours. After the reaction is completed, the temperature is lowered to room temperature and post-processed to obtain defective Cu(I)-based organic framework materials. The ternary acetylene monomer is selected from any of the substances shown in the following structural formulas: , or .

2. The defective Cu(I)-based organic framework material according to claim 1, characterized in that, The total molar ratio of the tri-alkynyl monomer and propargylamine in S1 to the molar ratio of copper tetrafluoroborate tetraacetonitrile is 0.3:1, wherein the amount of propargylamine is 20%-40% of the total molar ratio of the tri-alkynyl monomer and propargylamine.

3. The defective Cu(I)-based organic framework material according to claim 1, characterized in that, The ratio of copper tetrafluoroborate tetraacetonitrile to solvent is 1 mmol: 15-25 mL.

4. A defective Cu(I)-based organic framework material according to claim 1, characterized in that, The amount of triethylamine used in S2 is 1.0%-1.5% of the volume of the solvent in S1.

5. A defective Cu(I)-based organic framework material according to claim 2, characterized in that, The amount of propargylamine used in S1 is 30% of the total molar amount of the ternary alkynyl monomer and propargylamine.

6. A method for preparing a defective Cu(I)-based organic framework material as described in any one of claims 1-5.

7. The application of a defective Cu(I)-based organic framework material as described in any one of claims 1-5 as a catalyst for the carboxylation reaction of carbon dioxide with aromatic alkynes.

8. The application of the defective Cu(I)-based organic framework material according to claim 7 as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes, characterized in that, The aromatic acetylenic is a substance represented by any of the following structural formulas: , , , , , , or .

9. The application of the defective Cu(I)-based organic framework material according to claim 7 as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes, characterized in that, In the carboxylation reaction, the relationship between the amount of catalyst and aromatic yne is as follows: based on the Cu content in the defective Cu(I)-based organic framework material, the molar ratio of Cu to aromatic yne is 0.05-0.1:

1.

10. The application of the defective Cu(I)-based organic framework material according to claim 7 as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes, characterized in that, The carboxylation reaction was carried out at a temperature of 60-90℃, a CO2 pressure of 0.1 MPa, and a reaction time of 4-8 h.

Images