Ag-based organic framework material and preparation method and application thereof

Abstract

The invention belongs to the technical field of metal organic framework materials, and provides an Ag-based organic framework material and a preparation method and application thereof.The specific preparation method comprises the steps that silver-based cyclic trinuclear pyrazole aldehyde, 2, 4, 6-tris (4-aminophenyl)-1, 3, 5-triazine and 1H-pyrazole-4-formaldehyde serve as building monomers, benzyl alcohol and 1, 2-dichlorobenzene serve as solvents, and the Ag-based organic framework material is prepared through a hydrothermal method; the preparation method comprises the following steps of: mixing the raw materials with trifluoroacetic acid as a catalyst, freezing, degassing and sealing the obtained mixture, heating to room temperature, uniformly mixing and dispersing, and heating the obtained mixture at 60-70 DEG C to react for 6-10 hours; and after the reaction is finished, carrying out post-treatment to obtain the Ag-based organic framework material. The Ag-based organic framework material is used as a catalyst for synthesis of propiolic acid compounds through a CO2 carboxylation reaction and shows excellent catalytic activity, and the catalyst is high in structural stability, easy to recycle and capable of being recycled and has a wide development prospect.

Description

Technical Field

[0001] This invention belongs to the field of metal-organic framework materials technology, and relates to an Ag-based organic framework material, its preparation method and application. 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 synthesis of phenylpropynyl acids from CO2 via carboxylation is a cutting-edge and key research area. These products can serve as important organic intermediates for 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, phenylpropynyl acids can also be used as modifiers and intermediates in the preparation of high-performance polymer materials, bringing innovative possibilities to the field of materials science. This reaction not only achieves efficient CO2 conversion but also provides a green and sustainable pathway for the synthesis of high-value-added chemicals.

[0003] For the carboxylation reaction of CO2 with terminal alkynes, researchers have developed various homogeneous and heterogeneous catalytic systems. Homogeneous catalytic systems include metal-Salen complexes and ionic liquids; heterogeneous catalytic systems include transition metal-supported metal-organic frameworks (MOFs), covalent organic frameworks (COFs), ionic liquids, porous polymers, and functionalized carbon materials. Due to their unique structure and excellent properties, such as strong gas storage capacity, good chemical stability, and recyclability, metal-organic frameworks have become highly promising catalytic materials for CO2 carboxylation reactions. These materials can significantly improve reaction efficiency and selectivity, providing important theoretical and practical support for the practical application of CCU technology. Currently, metal-organic framework materials used for activating terminal alkynes include Cu(I)-based, Ag-based, and Au-based materials.

[0004] Homogeneous catalytic systems offer advantages such as high mass transfer rates, low preparation costs, and high product yields and selectivity. However, they also have significant drawbacks, namely, difficulty in separating the catalyst from the product and challenges in recycling. Heterogeneous catalytic systems, on the other hand, can be recovered and recycled through simple filtration and possess characteristics such as large specific surface area and high thermal stability. However, most heterogeneous catalysts currently reported suffer from problems such as complex preparation processes, poor structural stability, or low catalytic activity leading to harsh reaction conditions. For example, Chinese patent application CN 104117390 A discloses a method for preparing a metal-organic framework catalyst supported on silver nanoparticles, but this method is complex and exhibits low catalytic activity. For example, Zheng et al. (Zheng J., Wang JN, Wang T., et al. Phosphorescent Metal Rotaxane-like Bimetallic Ag / Au Clusters[J]. The Journal of Physical Chemistry C, 2021, 125(17): 9400-9410) reported a series of heterometallic Ag / Au clusters (Ag13-xAux-R, R=H, OMe, F) synthesized by solvent diffusion using 3-substituted phenylacetylene as a ligand. These clusters have a unique "wheel-axle" structure, consisting of a [Au@Ag 12 The core consists of a core and a protective shell composed of six 3,5-trifluoromethylpyrazolate groups and eight phenylethynyl ligands. These Ag / Au clusters can catalyze the carboxylation reaction of CO2 with aromatic end-acetylenes, but they suffer from problems such as high cost and insufficient structural stability.

[0005] In conclusion, the development of heterogeneous catalysts that combine high stability, high efficiency, and low cost is particularly urgent. Summary of the Invention

[0006] This invention proposes an Ag-based organic framework material, its preparation method, and its application. The Ag-based organic framework material has high catalytic activity, is easy to recycle and reuse, and its preparation method is simple. When used as a catalyst for the reaction of CO2 with aromatic yne under normal pressure, it has high yield and good selectivity.

[0007] The technical solution of this invention is implemented as follows: Technical Topic 1 An Ag-based organic framework material is prepared by a method comprising: mixing silver-based cyclotrinuclear pyrazolaldehyde [Ag3(PyCA)3], 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT), 1H-pyrazol-4-carboxaldehyde (HPyCA), a solvent, and trifluoroacetic acid; subjecting the resulting mixture to a freeze-vacuum-thaw cycle for degassing; sealing the mixture to a closed, oxygen-free environment; heating the mixture to room temperature; mixing and dispersing the mixture uniformly; and then heating the mixture at 60-70°C for 6-10 h; and after post-treatment, obtaining the Ag-based organic framework material.

[0008] Preferably, the total molar amount of the silver-based cyclotrinuclear pyrazolaldehyde and 1H-pyrazol-4-carboxaldehyde is in a molar ratio of 1:1 to that of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, wherein the molar amount of 1H-pyrazol-4-carboxaldehyde is 20%-50% of the molar amount of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, that is, the molar amount of 1H-pyrazol-4-carboxaldehyde is 20%-50% of the total molar amount of the silver-based cyclotrinuclear pyrazolaldehyde and 1H-pyrazol-4-carboxaldehyde.

[0009] Preferably, the molar amount of 1H-pyrazole-4-carboxaldehyde is 30% of the molar amount of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine; and the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to trifluoroacetic acid is 0.05 mmol:0.6 mmol.

[0010] Preferably, the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to trifluoroacetic acid is 0.05 mmol: 0.5-0.8 mmol.

[0011] Preferably, the trifluoroacetic acid is a 6 mol / L aqueous solution of trifluoroacetic acid; the ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to the aqueous solution of trifluoroacetic acid is 0.05 mmol: 0.1-0.12 mL.

[0012] Preferably, the solvent is benzyl alcohol and 1,2-dichlorobenzene in a volume ratio of 1:0.8-1.2.

[0013] Preferably, the ratio of the amount of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to the amount of solvent is 1 mmol: 18-22 mL.

[0014] Preferably, the ratio of the amounts of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to benzyl alcohol and 1,2-dichlorobenzene is 1 mmol: 10 mL: 8-12 mL.

[0015] Preferably, the mixing is performed using ultrasonic treatment, with an ultrasonic time of 20-40 minutes, an ultrasonic power of 100W-200W, and a frequency of 35-45 kHz.

[0016] Preferably, the post-processing includes the following steps: filtration, washing, solvent Soxhlet extraction, and drying.

[0017] Preferably, the drying step includes: vacuum drying at 50-80°C for 10-14 h.

[0018] Preferably, the solvent for Soxhlet extraction is selected from methanol, acetone, and tetrahydrofuran, and the extraction time is 12-24 hours.

[0019] Preferably, the preparation method of the silver-based cyclic trinuclear pyrazolaldehyde includes the following steps: 1 H A mixture of pyrazole-4-carboxaldehyde, silver benzoate, solvent, and triethylamine was stirred in a light-protected environment for 10-14 hours, washed, and dried to obtain silver-based cyclic trinuclear pyrazole aldehyde Ag3(PyCA)3. H The dosage relationship of pyrazole-4-carboxaldehyde, silver benzoate and triethylamine is 0.4-0.6 mmol: 0.4-0.6 mmol: 0.1-0.3 mL.

[0020] Preferred, 1 H The ratio of pyrazole-4-carboxaldehyde to solvent is 0.4-0.6 mmol: 14-16 mL.

[0021] Preferably, the solvent is tetrahydrofuran.

[0022] Preferably, the washing process involves sequentially washing with anhydrous ethanol and DMSO.

[0023] Technical Theme Two The present invention also provides a method for preparing the above-mentioned Ag-based organic framework material.

[0024] Technical Theme 3 The present invention also provides the application of the above-mentioned Ag-based organic framework material as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes.

[0025] Preferably, the aromatic yne has the following structural formula: , , , , , .

[0026] Preferably, the carboxylation reaction uses cesium carbonate as an auxiliary agent, and the ratio of the amount of aromatic yne, Ag-based organic framework material and cesium carbonate is: 1 mmol : 0.04-0.06 g : 1.2-1.8 mmol.

[0027] Preferably, the carboxylation reaction temperature is 30-60℃, the CO2 pressure is 0.1 MPa, and the reaction time is 6-14 h.

[0028] The beneficial effects of the present invention using the above technical solution are as follows: 1. The Ag-based organic framework material provided by this invention has the advantages of high catalytic activity, good structural stability, easy recycling, recyclability, and efficient and environmentally friendly synthesis.

[0029] 2. This invention provides a method for preparing Ag-based organic framework materials using a one-pot, three-component monomer reaction. This preparation method is characterized by its simplicity and high efficiency.

[0030] 3. This invention provides a method for using Ag-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

[0031] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0032] Figure 1 For Ag3(PyCA)3 1 H NMR spectrum.

[0033] Figure 2 For Ag3(PyCA)3 13 C NMR spectrum.

[0034] Figure 3 Cu3(PyCA)3 13 C NMR spectrum.

[0035] Figure 4 The diagrams show partial structural schematics of the different materials prepared, including (a) a partial structural schematic of AgL-MOF; and (b) a partial structural schematic of the Ag-based organic framework material prepared in this invention.

[0036] Figure 5 FTIR and solid-state reactions of different materials prepared for this invention 13C NMR comparison images, including (a) FTIR comparison images of TAPT, Ag3(PyCA)3, CuL-MOF and AgL-MOF; (b) FTIR comparison images of 10%AgB-MOF, 10%AgPD-MOF and 10%AgPZ-MOF; (c) FTIR comparison images of AgL-MOF, 10%AgPZ-MOF, 30%AgPZ-MOF and 50%AgPZ-MOF; (d) solid images of AgL-MOF and 30%AgPZ-MOF. 13 C NMR comparison image.

[0037] Figure 6 XPS spectra of AgL-MOF and 30%AgPZ-MOF of the present invention: (a) total spectrum; (b) C 1s; (c) N 1s; (d) Ag 3d.

[0038] Figure 7 The images show XRD patterns of different materials prepared according to the present invention, including: (a) XRD patterns of TAPT, Ag3(PyCA)3, CuL-MOF and AgL-MOF; (b) XRD patterns of 10%AgB-MOF, 10%AgPD-MOF, 10%AgPZ-MOF, 30%AgPZ-MOF and 50%AgPZ-MOF; (c) Simulation analysis of AA stacking of AgL-MOF catalyst; (d) Front and side views of AA stacking of AgL-MOF catalyst; (e) Simulation analysis of AB stacking of AgL-MOF catalyst; and (f) Front and side views of AB stacking of AgL-MOF catalyst.

[0039] Figure 8 These are scanning electron microscope images of AgL-MOF and 30%AgPZ-MOF of the present invention, wherein (ac) AgL-MOF; (df) 30%AgPZ-MOF; and (gj) 30%AgPZ-MOF SEM mapping image.

[0040] Figure 9 This is a graph showing the catalytic performance evaluation of the 30% AgPZ-MOF catalyst for the carboxylation reaction of carbon dioxide with different aromatic alkynes according to the present invention.

[0041] Figure 10 The following is a cyclic performance evaluation diagram of the 30%AgPZ-MOF catalyst used in the carboxylation reaction of carbon dioxide and aromatic alkynes according to the present invention, wherein (a) is a cyclic performance diagram; and (b) is an FTIR spectrum of 30%AgPZ-MOF before and after cycling. Detailed Implementation

[0042] 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.

[0043] 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.

[0044] In the following examples and comparative examples, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 1H-pyrazole-4-carboxaldehyde (HPyCA) are commercially available.

[0045] Example 1 Ligand 1 H A mixture of pyrazole-4-carboxaldehyde (HPyCA, 48 mg, 0.5 mmol), silver benzoate (85 mg, 0.5 mmol), 15 mL of tetrahydrofuran, and 0.2 mL of triethylamine was added to a 50 mL single-necked flask. The resulting mixture was then stirred in the dark for 12 hours. The mixture was washed with anhydrous ethanol, and the reduced black Ag particles were washed away with DMSO. After drying, a white solid silver-based cyclic trinuclear pyrazole aldehyde, namely Ag3(PyCA)3 (94.07 mg, yield 71.5% based on silver benzoate), was obtained.

[0046] like Figure 1 , Figure 2 and Figure 5 As shown in (a), using 1 H NMR, 13 The Ag3(PyCA)3 was characterized by C NMR and FTIR, and the results are as follows: 1 H NMR (400 MHz, 300 K, DMSO- d6) δ (ppm) 9.84 (s, 1H), 8.20 (s, 2H). 13 C NMR (100 MHz, CDCl3) δ (ppm): 185.13, 144.12, 122.57. FT-IR(KBr),γ max / cm -1 : 1660 (-CHO).

[0047] Example 2 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (0.035 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.015 mmol, with HPyCA being 30% of the molar amount of TAPT) were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.5 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three cycles of freezing-vacuuming-thawing, the ampoule was flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature, ultrasonically treated (150 W, 40 kHz) for 30 min to achieve uniform dispersion, heated at 65 °C for 8 h, and filtered to obtain a yellow-green solid. This solid was purified by washing and Soxhlet extraction with methanol for 20 h, and then vacuum-dried at 60 °C for 12 h to obtain a yellow-green powder (30% AgPZ-MOF).

[0048] Example 3 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (0.04 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.48 mg, 0.01 mmol, with HPyCA being 20% ​​of the molar amount of TAPT) were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.5 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three freeze-vacuum-thaw cycles, the ampoule was flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature, ultrasonicated (150 W, 40 kHz) for 30 min to ensure uniform dispersion, heated at 65 °C for 8 h, and filtered to obtain a yellow-green solid. This solid was purified by washing and Soxhlet extraction with methanol for 20 h, and then vacuum-dried at 60 °C for 12 hours. h, yielded a yellow-green powder 20% AgPZ-MOF.

[0049] Example 4 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (0.025 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.025 mmol, with HPyCA being 50% of the molar amount of TAPT) were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.5 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three freeze-vacuum-thaw cycles, the ampoule was flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature, ultrasonically dispersed (150 W, 40 kHz) for 30 min, heated at 65 °C for 8 h, and filtered to obtain a yellow-green solid. This solid was purified by washing and Soxhlet extraction with methanol for 20 h, and then vacuum-dried at 60 °C for 12 h. h, yielded a yellow-green powder 50% AgPZ-MOF.

[0050] Example 5 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (0.035 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.015 mmol, with HPyCA being 30% of the molar amount of TAPT) were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.4 mL of 1,2-dichlorobenzene, and 0.12 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three cycles of freezing-vacuuming-thawing, the ampoule was flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature, ultrasonicated (120 W, 45 kHz) for 20 min to ensure uniform dispersion, heated at 70 °C for 6 h, and filtered to obtain a yellow-green solid. After washing and Soxhlet extraction with tetrahydrofuran for 12 h for purification, the solid was vacuum-dried at 80 °C for 10 h to obtain a yellow-green powder.

[0051] Example 6 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (0.035 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.015 mmol, with HPyCA being 30% of the molar amount of TAPT) were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.6 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three freeze-vacuum-thaw cycles, the ampoule was flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature and ultrasonically treated (120 W, 40 kHz) for 40 min to achieve uniform dispersion. After heating at 60 °C for 10 h, the mixture was filtered to obtain a yellow-green solid. Following washing and Soxhlet extraction with acetone for 24 h for purification, the solid was vacuum-dried at 50 °C for 14 h to obtain a yellow-green powder.

[0052] Comparative Example 1 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (30.5 mg, 0.05 mmol) and TAPT (17.7 mg, 0.05 mmol) synthesized in Example 1 were added to a 10 mL ampoule. Then, 0.5 mL of benzyl alcohol, 0.5 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoule. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K), degassed by three freeze-vacuum-thaw cycles, and then flame-sealed to ensure a closed, oxygen-free environment. The mixture was then heated to room temperature and ultrasonically treated (150 W, 40 kHz) for 30 min to achieve uniform dispersion. After heating at 65 °C for 8 h, the yellow-green solid was separated by filtration. Following washing and Soxhlet extraction with methanol for 20 h, the solid was vacuum-dried at 60 °C for 12 h to obtain a yellow-green powder, AgL-MOF (35.2 mg, 73% yield).

[0053] Comparative Example 2 In a 25 mL pressure-resistant bottle, copper nitrate trihydrate (0.20 g, 0.83 mmol) and 1 H4-Pyrazole-4-carboxaldehyde (HPyCA, 0.096 g, 1.0 mmol) was dissolved in a mixed solvent containing 6.7 mL DMF, 5.0 mL H2O, and 6.7 mL anhydrous ethanol. The pressure-resistant bottle was sealed and placed in an oven at 100 °C for static reaction for 12 h, yielding a pale yellow crystalline solid. The solid was collected and immersed in H2O for three days, during which H2O was exchanged three times daily. The crystals were then rapidly washed three times with acetone and dried under vacuum at 120 °C for 24 h to obtain pale yellow crystalline Cu3(PyCA)3 (94.07 mg, yield 73% based on copper nitrate trihydrate).

[0054] like Figure 3 ,use 13 The Cu3(PyCA)3 was characterized by C NMR, and the data are as follows: 13 C NMR (100 MHz, CDCl3) δ (ppm): 186.01, 145.96, 122.90.

[0055] A method for preparing a Cu-based organic framework material includes the following steps: Similar to Comparative Example 1, except that Ag3(PyCA)3 (30.5 mg, 0.05 mmol) was replaced with Cu3(PyCA)3 (23.8 mg, 0.05 mmol) in Comparative Example 1. The reaction process was the same as in Comparative Example 1. After the reaction was completed, the orange solid was separated by filtration. After washing and Soxhlet extraction with methanol for 20 hours for purification, the solid was vacuum dried at 60 °C for 12 h to obtain orange powder CuL-MOF (28.8 mg, yield 88%).

[0056] Comparative Example 3 A method for preparing an Ag-based organic framework material includes the following steps: Ag3(PyCA)3 (27.4 mg, 0.045 mmol), TAPT (17.7 mg, 0.05 mmol), and HPyCA (0.48 mg, 0.005 mmol, with HPyCA being 10% of the molar amount of TAPT) were added to 10 mL ampoules. Then, 0.5 mL of benzyl alcohol, 0.5 mL of 1,2-dichlorobenzene, and 0.1 mL of 6 M trifluoroacetic acid were added sequentially to the ampoules. The resulting mixture was rapidly frozen in a liquid nitrogen bath (77 K). After degassing through three freeze-vacuum-thaw cycles, the ampoules were flame-sealed to create a closed, oxygen-free environment. The mixture was then heated to room temperature and ultrasonically dispersed (150 W, 40 kHz) for 30 min. After heating at 65 °C for 8 h, the yellow-green solid was separated by filtration. Following washing and Soxhlet extraction with methanol for 20 h, the solid was vacuum-dried at 60 °C for 12 hours. h, yielded a yellow-green powder 10% AgPZ-MOF.

[0057] Comparative Example 4 Similar to Comparative Example 3, except that HPyCA (0.48 mg, 0.005 mmol) was replaced with pyridine-4-carboxaldehyde (0.535 mg, 0.005 mmol), and all other synthetic steps were the same as those in Comparative Example 3 to prepare 10% AgPD-MOF.

[0058] Comparative Example 5 Similar to Comparative Example 3, except that HPyCA (0.48 mg, 0.005 mmol) was replaced with benzaldehyde (0.25 mg, 0.005 mmol), and all other synthesis steps were the same as those in Comparative Example 3 to prepare 10% AgB-MOF.

[0059] Test case structure representation like Figure 5 FTIR and solid-state tests of different materials prepared in this invention 13 C NMR comparison images, including (a) FTIR comparison images of TAPT, Ag3(PyCA)3, CuL-MOF and AgL-MOF; (b) FTIR comparison images of 10%AgB-MOF, 10%AgPD-MOF and 10%AgPZ-MOF; (c) FTIR comparison images of AgL-MOF, 10%AgPZ-MOF, 30%AgPZ-MOF and 50%AgPZ-MOF; (d) solid images of AgL-MOF and 30%AgPZ-MOF. 13 C NMR comparison diagram. (See figure) Figure 5As shown in (d), the aldehyde carbon signal at 180 ppm disappears, and an imine carbon signal peak appears at 160 ppm, further proving the formation of a new C=N bond and confirming the successful synthesis of the material.

[0060] like Figure 6 The above are XPS spectra of AgL-MOF and 30%AgPZ-MOF of the present invention: (a) total spectrum; (b) C 1s; (c) N 1s; (d) Ag 3d. Figure 6 (a) XPS spectra show that both AgL-MOF and 30%AgPZ-MOF are composed of carbon (C), nitrogen (N), and silver (Ag); Figure 6 (b) The C 1s curves of both materials can be divided into two peaks: CC / C=C and CN, corresponding to 284.8 eV and 285.8 eV respectively. However, the CN diffraction peak of the triazine ring in 30% AgPZ-MOF is at 286.1 eV, a decrease of 0.3 eV in binding energy compared to AgL-MOF. Figure 6 (c) shows that AgL-MOF exhibits a CN=C diffraction peak in pyrazole at 399.1 eV and an N-Ag diffraction peak in the Ag ring trinuclear structure at 401.0 eV. The N 1s spectrum of 30% AgPZ-MOF also fits these two peaks, but at a 0.2 eV higher level than AgL-MOF. Similarly, as... Figure 6 (d) shows that both materials are fitted with Ag3d. 3 / 2 and Ag 3d 5 / 2 The two peaks in AgL-MOF correspond to 368.8 eV and 374.6 eV respectively, but the 30%AgPZ-MOF is 0.1 eV lower than AgL-MOF. This shows that C, N and Ag have all shifted after the introduction of HPyCA material, which proves that the interaction has changed and that HPyCA has been successfully introduced into the material.

[0061] like Figure 7The figures show XRD comparisons of different materials prepared according to the present invention, including: (a) XRD patterns of TAPT, Ag3(PyCA)3, CuL-MOF, and AgL-MOF; (b) XRD patterns of 10%AgB-MOF, 10%AgPD-MOF, 10%AgPZ-MOF, 30%AgPZ-MOF, and 50%AgPZ-MOF; (c) Simulation analysis of AgL-MOF catalyst AA stacking; (d) Front and side views of AgL-MOF catalyst AA stacking; (e) Simulation analysis of AgL-MOF catalyst AB stacking; and (f) Front and side views of AgL-MOF catalyst AB stacking. Simulations were performed on both AA and AB stacking configurations of the AgL-MOF catalyst. The simulations showed that the material preferred AB stacking, with distinct diffraction peaks observed around 4.3°, 7.5°, 8.3°, 11.8°, and 27.7°, corresponding to the (100), (110), (200), (120), and (001) crystal planes of AgL-MOF, respectively. These peaks largely matched the simulated peaks, further confirming the successful synthesis of the material.

[0062] like Figure 8 The images shown are scanning electron microscope (SEM) images of AgL-MOF and 30%AgPZ-MOF of this invention, where (ac) is AgL-MOF; (df) is 30%AgPZ-MOF; and (gj) is the SEM mapping image of 30%AgPZ-MOF. Figure 8 As shown in (ac), the two materials exhibit strip-like morphologies at 500 nm, 1 μm, and 5 μm. Analysis of the 30% AgPZ-MOF EDS mapping spectrum reveals... Figure 8 (gj) It can be seen that C, N, and Ag elements are uniformly distributed on the catalyst surface in 30%AgPZ-MOF.

[0063] Application example: Catalytic application of CO2 in the carboxylation reaction of aromatic alkynes 1. Evaluation of catalytic performance in the carboxylation reaction with phenylacetylene In a 25 mL Schlenk tube, 0.2 mmol of phenylacetylene, 0.3 mmol of 1.5 equiv Cs₂CO₃, 0.01 g of catalyst, and 1 mL of anhydrous DMF were added sequentially. The Schlenk tube was sealed with a stopper and subjected to a freeze-evacuation-thawing cycle to remove air from the tube. It was then connected to an atmospheric pressure CO₂ balloon, and the reaction was stirred at a predetermined temperature for a certain time. After the reaction was complete, it was cooled to room temperature. The catalyst was separated by vacuum filtration, and the filtrate was diluted with water (15 mL) and extracted with dichloromethane (3 × 20 mL). The aqueous phase was acidified to pH 1 with 1 M hydrochloric acid, and then extracted three times with ethyl acetate (3 × 20 mL). The combined organic phase was washed with saturated NaCl solution, dried over anhydrous Na₂SO₄, and filtered. The solvent was removed by vacuum rotary evaporation to obtain the product. The reaction equation is as follows: Table 1 shows the catalytic performance of different materials prepared in this invention as catalysts for the carboxylation of CO2 and aromatic alkynes. The results show that when Cs2CO3 and 30%AgPZ-MOF are used alone as catalysts, the yields of phenylpropynic acid are low, at 13% and 27%, respectively. When different monomers Ag3(PyCA)3, TAPT, and HPyCA react with Cs2CO3, the product yields are very low, at 17%, 14%, and 13%, respectively. Using the 30%AgPZ-MOF / Cs2CO3 catalytic system, the yield can reach over 82% after reacting with CO2 for 12 h under ambient temperature and pressure. Extending the reaction time to 14 h further increases the yield to 93%. The special activity of this catalytic system can be attributed to the Ag in the 30%AgPZ-MOF structure, the N atom in the triazine ring and the pyrazole N atom, and the Cs in Cs2CO3. 2- The synergistic interaction between them simultaneously activates CO2 and phenylacetylene, thereby promoting their carboxylation reaction. It is evident that inorganic K2CO3 and Cs2CO3 are effective bases for catalyzing carboxylation reactions; however, only the use of Cs2CO3 yields good results.

[0064] Table 1 2. Recycling performance The 30% AgPZ-MOF catalyst was separated by vacuum filtration, and the solid was collected. To assess the catalyst's recyclability, the recovered 30% AgPZ-MOF catalyst was washed with dichloromethane and ethyl acetate, dried under vacuum at 80 °C for 6 h, and directly reused in subsequent catalytic reactions. The catalytic reaction conditions remained the same as those corresponding to item 14 in Table 1.

[0065] like Figure 10The figures show the cyclic performance evaluation of 30% AgPZ-MOF as a catalyst for the carboxylation reaction of carbon dioxide and aromatic alkynes, as presented in this invention. (a) shows the cyclic performance; (b) shows the FTIR of 30% AgPZ-MOF before and after cycling. It can be seen that after five cycles, the product yield did not decrease significantly. Based on the FTIR spectra before and after cycling, the catalyst exhibits excellent structural stability.

[0066] Similarly, the catalysts of Examples 2-6 were subjected to the same recycling verification. After five cycles, the product yield did not decrease significantly, demonstrating excellent structural stability.

[0067] 3. Determine the universality and the reaction results with different aromatic alkynes. In a 25 mL Schlenk tube, aromatic alkyne (0.2 mmol), 1.5 equiv Cs₂CO₃ (0.3 mmol), 30% AgPZ-MOF (0.01 g), and anhydrous DMF (1 mL) were added sequentially. The Schlenk tube was sealed with a stopper and subjected to a freeze-evacuation-thawing cycle to remove air from the tube. It was then connected to an atmospheric pressure CO₂ balloon and reacted at 30 °C with stirring for 14 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 × 20 mL). The aqueous phase was acidified to pH 1 with 1 M hydrochloric acid and then extracted three times with ethyl acetate (3 × 20 mL). The bound organic phase was washed with saturated NaCl solution, dried over anhydrous Na₂SO₄, and filtered. The solvent was removed by vacuum rotary evaporation to obtain the product.

[0068] like Figure 9 This figure shows the catalytic performance evaluation of the carboxylation reaction of carbon dioxide with different aromatic alkynes using the 30% AgPZ-MOF catalyst of this invention. Studies on the substrate scope indicate that the 30% AgPZ-MOF / Cs2CO3 catalytic system has good versatility.

[0069] 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. An Ag-based organic framework material, characterized in that, Preparation methods include: Silver-based cyclotrinuclear pyrazolaldehyde, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 1H-pyrazol-4-carboxaldehyde, solvent, and trifluoroacetic acid were mixed. The resulting mixture was subjected to a freeze-vacuum-thaw cycle for degassing, and then sealed to place the mixture in a closed, oxygen-free environment. The mixture was then heated to room temperature and mixed and dispersed evenly. Subsequently, the mixture was heated at 60-70℃ for 6-10 h. After the reaction was completed, Ag-based organic framework materials were obtained through post-treatment.

2. The Ag-based organic framework material according to claim 1, characterized in that, The total molar ratio of the silver-based cyclotrinuclear pyrazolaldehyde and 1H-pyrazol-4-carboxaldehyde to the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine is 1:1, wherein the molar ratio of 1H-pyrazol-4-carboxaldehyde is 20%-50% of the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine; the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to trifluoroacetic acid is 0.05 mmol: 0.5-0.8 mmol.

3. An Ag-based organic framework material according to claim 2, characterized in that, The molar amount of 1H-pyrazole-4-carboxaldehyde is 30% of the molar amount of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine; the molar ratio of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine to trifluoroacetic acid is 0.05 mmol:0.6 mmol.

4. The Ag-based organic framework material according to claim 1, characterized in that, The solvent is benzyl alcohol and 1,2-dichlorobenzene in a volume ratio of 1:0.8-1.2, and the amount of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine in benzyl alcohol and 1,2-dichlorobenzene is 1 mmol: 10 mL: 8-12 mL.

5. An Ag-based organic framework material according to claim 1, characterized in that, The preparation method of the silver-based cyclic trinuclear pyrazolaldehyde includes the following steps: 1 H A mixture of pyrazole-4-carboxaldehyde, silver benzoate, solvent, and triethylamine was stirred in a light-protected environment for 10-14 hours, washed, and dried to obtain silver-based cyclic trinuclear pyrazole aldehyde. The mixture, in part 1... H The dosage relationship of pyrazole-4-carboxaldehyde, silver benzoate and triethylamine is 0.4-0.6 mmol : 0.4-0.6 mmol : 0.1-0.3 mL.

6. A method for preparing the Ag-based organic framework material as described in any one of claims 1-5.

7. The application of an Ag-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 Ag-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 structural formula of the aromatic alkyne is as follows: ， ， ， ， ， 。 9. The application of the Ag-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 uses cesium carbonate as an auxiliary agent, and the ratio of the aromatic yne, Ag-based organic framework material to cesium carbonate is: 1 mmol : 0.04-0.06 g : 1.2-1.8 mmol.

10. The application of the Ag-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 is carried out at a temperature of 30-60℃, a CO2 pressure of 0.1 MPa, and a reaction time of 6-14 h.

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