Honeycomb-shaped novel COF functionalized silicon-based chromatographic stationary phase as well as preparation method and application of honeycomb-shaped novel COF functionalized silicon-based chromatographic stationary phase

Abstract

The invention relates to a honeycomb-shaped novel COF (Covalent Organic Framework) functionalized silicon-based chromatographic stationary phase. Silica gel is used as a matrix, and TAPT (Triallyl Phosphate) and DMTP (Dimethyl Tricarbonyl Phosphate) are subjected to aldehyde amine condensation reaction to form a two-dimensional The synthesis method comprises the following steps: activating silica gel particles by using hydrochloric acid, and neutralizing gamma-GPTS by using the activated spherical silica gel particles and anhydrous toluene to synthesize SiO2-GPTS; tAPT and DMTP are used as raw materials, a two-dimensional covalent organic framework COF is formed through a Schiff base aldehyde amine condensation reaction, and a novel honeycomb-shaped COF functionalized silicon-based chromatographic stationary phase SiO2 (at) TAPT-DMTP-COF is formed through coordination of silicon hydroxyl and amino / aldehyde group of a COF skeleton. When the TAPT-DMTP-COF is applied to chromatographic column separation, the TAPT-DMTP-COF has a porous structure with plane pi conjugation, height orderliness and stability, and the specific structure of the TAPT-DMTP-COF enables fixed relative shape limited isomers, geometric isomers and positional isomers to show excellent selectivity and separation capacity; the surface of SiO2 is coated with the COF-modified high performance liquid chromatography stationary phase material, so that the COF-modified high performance liquid chromatography stationary phase material has a uniform honeycomb shape, and a new way is opened up for constructing the COF-modified high performance liquid chromatography (HPLC) stationary phase material with the uniform shape.

Description

Technical Field:

[0001] The present invention relates to the technical field of chromatographic stationary phase synthesis, and specifically relates to a honeycomb-shaped novel COF-functionalized silica-based chromatographic stationary phase, its preparation method and application. Background Art:

[0002] The performance of the chromatographic stationary phase directly determines the separation selectivity and efficiency. With the increasing demand for the analysis of complex samples, traditional chromatographic stationary phases have limitations in separating certain special substances. For example, the separation effect of shape-constrained isomers is not good. Silica-based chromatographic stationary phases have been widely studied and applied due to their good mechanical properties and chemical stability. However, their limited chemical diversity and pore size distribution are difficult to meet the high-efficiency separation requirements of complex isomers, and there are problems such as insufficient selectivity, slow mass transfer rate, and low column efficiency when separating structurally similar compounds. Covalent organic frameworks (COFs) are a class of materials with highly ordered porous structures, having good chemical stability and designability. Functionalizing COF onto the silica-based stationary phase can combine the mechanical properties of the silica-based material and the porous structure advantages of COF, thereby improving the separation selectivity and efficiency of the stationary phase. However, physical adsorption or simple mixing will cause the COF layer to fall off, and at the same time, its uniform loading on the silica gel surface and morphology control are still technical difficulties. Therefore, the research and development of novel liquid chromatography stationary phases with excellent performance are of great significance for overcoming the deficiencies of traditional stationary phases and meeting the high-selectivity separation of shape-constrained isomers. Summary of the Invention:

[0003] Aiming at the above problems, the present invention provides a honeycomb-shaped novel COF-functionalized silica-based chromatographic stationary phase, its preparation method and application, providing a general method for synthesizing COF-modified stationary phases with uniform morphology; and overcoming the limitations of traditional silica-based chromatographic stationary phases, reducing the mass transfer resistance during the separation of shape isomers, improving the molecular recognition ability, thereby improving the separation efficiency and selectivity of isomers.

[0004] A honeycomb-shaped novel COF-functionalized silica-based chromatographic stationary phase, the honeycomb-shaped novel COF-functionalized silica-based chromatographic stationary phase uses silica gel as a matrix, and uses 2,4,6-tris(4-aminophenyl)-1,3,5-triazine TAPT and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde DMTP as raw materials, and in-situ grows a two-dimensional covalent organic framework COF on the silica gel through a Schiff base aldehyde-amine condensation reaction to form a honeycomb-shaped novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF. The structure of the honeycomb-shaped novel SiO2@TAPT-DMTP-COF chromatographic stationary phase is:

[0005]

[0006] Preferably, the silica gel matrix is spherical, with a particle size of 5 - 6 μm, a pore size of 8 - 15 nm, and a specific surface area of 300 m 2 g -1 .

[0007] Preferably, the dosage of TAPT-DMTP-COF contained in each gram of the silica gel matrix is 0.2 - 1.5 g.

[0008] Preferably, the COF contains a covalent triazine structure, and TAPT-DMTP-COF self-assembles and grows on the silica gel surface to form a dense honeycomb-like porous structure coating layer.

[0009] A preparation method of a honeycomb-like novel COF-functionalized silica-based chromatographic stationary phase, the method specifically being:

[0010] Step 1: Silica gel activation: Disperse the unactivated silica gel particles in a hydrochloric acid solution according to a certain mass ratio, heat and stir under reflux for 7 - 9 h, cool to room temperature, wash by centrifugation with deionized water multiple times until neutral, and then dry at 120 - 130 °C for 12 - 24 h;

[0011] Step 2: Preparation of γ-glycidoxypropyl group-modified SiO₂: Disperse the activated spherical silica gel particles in anhydrous toluene according to a certain ratio, add a silane coupling agent, reflux and stir in a nitrogen atmosphere for 12 - 24 h, then cool to room temperature, filter, and wash 3 times each with toluene, ethanol, and acetone, and dry at 60 - 100 °C for 12 - 24 h to obtain the modified SiO₂, and the silane coupling agent has a γ-glycidoxypropyl group;

[0012] Step 3: Synthesis of the SiO₂@TAPT-DMTP-COF chromatographic stationary phase: Disperse 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde in an acetonitrile solution according to a certain molar ratio; successively add the modified SiO₂ and acetic acid, and let it stand at room temperature for 24 - 72 h; after standing, wash by centrifugation successively with tetrahydrofuran and ethanol, and dry at 65 - 75 °C for 12 - 16 h to obtain the honeycomb-like novel COF-functionalized silica-based chromatographic stationary phase SiO₂@TAPT-DMTP-COF.

[0013] Preferably, in Step 1, the concentration of hydrochloric acid for activating the silica gel is 3 mol / L; the temperature for heating under reflux is 100 - 120 °C.

[0014] Preferably, in Step 2, the ratio of the activated silica gel, anhydrous toluene, and the silane coupling agent is 1 g:(10 - 20) mL:(3 - 4) mL, and the silane coupling agent with a γ-glycidoxypropyl group is γ-glycidoxypropyltrimethoxysilane.

[0015] Preferably, in the third step, the molar ratio of TAPT to DMTP is (0.035 - 0.055) mmol:(0.070 - 0.10) mmol, and the addition ratio of acetonitrile, acetic acid and SiO2-GPTS is (5.0 - 7.0) mL:(0.50 - 0.65) mL:(30.0 - 50.0) mg; the acetic acid is used as a catalyst in the reaction system, and its concentration is 4 - 7 mol / L.

[0016] A novel honeycomb COF-functionalized silica-based chromatographic stationary phase is applied to separate hydrophobic compounds, polar compounds, shape-restricted isomers and position isomers in the reversed-phase chromatography mode in the HPLC mode, and to separate nucleoside and nucleobase compounds in the HILIC and PALC modes.

[0017] Preferably, the hydrophobic compound is alkylbenzene; the polar compound is aniline analyte; the shape-restricted isomers include polycyclic aromatic hydrocarbons (PAHs), tocopherol isomers (α-, β-, γ-, δ-), carotenoid isomers (lutein, lycopene, α-, β-carotene); the position isomers include xylene, dichlorobenzene, nitroaniline, chloronitrobenzene.

[0018] The present invention designs a novel honeycomb COF-functionalized silica-based chromatographic stationary phase and its preparation method and application. The SiO2@TAPT-DMTP-COF stationary phase can simultaneously be compatible with three separation modes of reversed-phase chromatography (RPLC), hydrophilic interaction chromatography (HILIC) and water-rich chromatography (PALC) through its unique chemical composition and pore design. Compared with traditional single-mode stationary phases, it can reduce the complexity of the analysis process. A single chromatographic column can separate complex samples with a large polarity span (such as simultaneously analyzing the hydrophobic aglycone and hydrophilic metabolites in drugs), avoiding multi-column switching or gradient elution. At the same time, by adjusting the proportion of the mobile phase, the retention mechanism of the stationary phase is dynamically regulated, which is suitable for multi-scenario requirements such as drug impurity analysis and environmental pollutant screening. The self-assembled monolayer-assisted surface-initiated polycondensation method proposed by the present invention overcomes the technical problem of the uniform loading of COF on the silica surface. Through the pretreatment of the silica surface amination and the regulation of the solvothermal reaction kinetics, the COF layer grows epitaxially along the silica surface, forming a honeycomb coating layer with a uniform thickness, a unique pore structure and a high specific surface area, overcoming the traditional C 18The problem of slow mass transfer rate in the column. The COF framework is firmly bonded to the silica matrix through a hydrogen bond network and Si-O-C covalent bonds, improving the stability of the stationary phase. The high-rigid π-conjugated system, abundant hydrophobic alkyl chains and benzene rings in the TAPT-DMTP-COF framework provide the possibility for the formation of hydrophobic interactions and π-π interactions between the stationary phase and aromatic solute molecules; the abundant imine bonds and terminal -NH2 can form hydrogen bond interactions with isomer molecules as donors or acceptors of hydrogen bonds; the hydrophilic triazine ring and amino group present promote the formation of a water-rich layer on the surface of the stationary phase, having a hydrophilic retention mechanism; thus, the prepared stationary phase shows high selectivity and separation ability for shape-constrained isomers and positional isomers. Description of the Drawings:

[0019] Attached Figure 1 is a schematic structural diagram of the novel honeycomb COF-functionalized silica-based chromatographic stationary phase disclosed in the present invention. Attached Figure 2 is a flow chart of the preparation method of a novel honeycomb COF-functionalized silica-based chromatographic stationary phase disclosed in the present invention.

[0020] Attached Figure 3 is the XRD pattern of the novel honeycomb COF-functionalized silica-based chromatographic stationary phase prepared in Example 3 of the present invention.

[0021] Attached Figure 4 is the SEM image of the novel honeycomb COF-functionalized silica-based chromatographic stationary phase prepared in Example 3 of the present invention.

[0022] Attached Figure 5 is the thermogravimetric characterization diagram of the novel honeycomb COF-functionalized silica-based chromatographic stationary phase prepared in Example 3 of the present invention.

[0023] Attached Figure 6 is the chromatogram of Application Example 1 of the present invention.

[0024] Attached Figure 7 is the chromatogram of Application Example 2 of the present invention.

[0025] Attached Figure 8 is the chromatogram of Application Example 3 of the present invention.

[0026] Attached Figure 9 is the chromatogram of Application Example 4 of the present invention.

[0027] Attached Figure 10 is the chromatogram of Application Example 5 of the present invention. Detailed Embodiments:

[0028] In order to make the technical solution of the present invention easier to understand, a preparation method of a novel honeycomb COF-functionalized silica-based chromatographic stationary phase disclosed in the present invention is clearly and completely described in the form of embodiments and drawings.

[0029] Example 1:

[0030] (1) Silica gel activation: Weigh 3.0 g of SiO2 (5 μm) particles and put them into a 100 mL round-bottom flask. Then add 60 mL of 3M HCl solution, ultrasonically disperse for 1 min, heat under reflux at 100 °C for 7 h, cool to room temperature, and repeatedly centrifuge and wash with deionized water for multiple times until the pH value of the supernatant is close to neutral. Then dry at 120 °C for 12 h to obtain activated silica gel;

[0031] (2) Preparation of SiO2-GPTS: According to the ratio of activated SiO2: γ-GLDP: anhydrous toluene = 1 g: 3 mL: 20 mL, mix them and ultrasonically disperse evenly. Then repeatedly evacuate and fill with N2, reflux and stir in an N2 atmosphere for 12 h, cool to room temperature and filter. Wash with toluene, ethanol, and acetone three times each, and then dry in an oven at 60 °C for 24 h to obtain modified silica gel SiO2-GPTS;

[0032] (3) Synthesis of SiO2@TAPT-DMTP-COF chromatographic stationary phase: Disperse 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) in a glass vial containing 5 mL of ACN solution according to the ratio of 0.035 mmol: 0.07 mmol; then successively add 30 mg of SiO2-GPTS and 0.5 mL of 7 mol / L acetic acid, ultrasonically treat for 1 min to obtain a uniform suspension, and let it stand and react at room temperature for 24 h; after the reaction is completed, centrifuge and wash with THF and C2H5OH three times each, and dry at 65 °C for 16 h to obtain a novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF with a honeycomb morphology, namely Sample 1.

[0033] Example 2:

[0034] (4) Silica gel activation: Weigh 3.0 g of SiO2 (5 μm) particles and put them into a 100 mL round-bottom flask. Then add 60 mL of 3M HCl solution, ultrasonically disperse for 1 min, heat under reflux at 110 °C for 8 h, cool to room temperature, and repeatedly centrifuge and wash with deionized water for multiple times until the pH value of the supernatant is close to neutral. Then dry at 125 °C for 18 h to obtain activated silica gel;

[0035] (5) Preparation of SiO2-GPTS: According to the ratio of activated SiO2: γ-GLDP: anhydrous toluene = 1 g: 3.5 mL: 15 mL, mix them and disperse evenly by ultrasonic treatment. Then repeatedly evacuate and fill with N2, reflux and stir for 18 h under N2 atmosphere. After cooling to room temperature, filter, wash three times with toluene, ethanol, and acetone in sequence, and then dry in an oven at 80 °C for 16 h to obtain modified silica gel SiO2-GPTS;

[0036] (6) Synthesis of SiO2@TAPT-DMTP-COF chromatographic stationary phase: Disperse 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dimethoxybenzene-1,4-dicarbaldehyde (DMTP) in a glass vial containing 6 mL of ACN solution according to the ratio of 0.045 mmol: 0.085 mmol. Then add 40 mg of SiO2-GPTS and 0.55 mL of 6 mol / L acetic acid in sequence, and ultrasonically treat for 1 min to obtain a uniform suspension. Let it stand and react at room temperature for 48 h. After the reaction, centrifuge and wash three times with THF and C2H5OH in sequence, and dry at 70 °C for 14 h to obtain a novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF with a honeycomb-like morphology, that is, sample 2.

[0037] Example 3:

[0038] (7) Silica gel activation: Weigh 3.0 g of SiO2 (5 μm) particles and put them into a 100 mL round-bottom flask. Then add 60 mL of 3 M HCl solution, disperse by ultrasonic treatment for 1 min, heat and reflux at 120 °C for 7 h, cool to room temperature, and repeatedly centrifuge and wash with deionized water until the pH value of the supernatant is close to neutral. Then dry at 130 °C for 24 h to obtain activated silica gel;

[0039] (8) Preparation of SiO2-GPTS: According to the ratio of activated SiO2: γ-GLDP: anhydrous toluene = 1 g: 4 mL: 20 mL, mix them and disperse evenly by ultrasonic treatment. Then repeatedly evacuate and fill with N2, reflux and stir for 24 h under N2 atmosphere. After cooling to room temperature, filter, wash three times with toluene, ethanol, and acetone in sequence, and then dry in an oven at 100 °C for 12 h to obtain modified silica gel SiO2-GPTS;

[0040] (9)Synthesis of SiO2@TAPT-DMTP-COF chromatographic stationary phase: Disperse 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) in a glass vial containing 7 mL of ACN solution at a ratio of 0.055 mmol:0.1 mmol; then successively add 50 mg of SiO2-GPTS and 0.65 mL of 4 mol / L acetic acid, and ultrasonically treat for 1 min to obtain a uniform suspension, and let it stand and react at room temperature for 72 h; after the reaction, centrifuge and wash 3 times each with THF and C2H5OH, and dry at 75 °C for 12 h to obtain a novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF with a honeycomb-like morphology, namely sample 3. The synthesis process is as Figure 2 shown, and the product structure is as Figure 1 shown.

[0041] Table 1 Elemental analysis table of the novel COF-functionalized silica-based chromatographic stationary phase with a honeycomb-like morphology

[0042] Sample N(％) C(％) H(％) <![CDATA[SiO2-GPTS]]> 0 5.66 1.59 <![CDATA[SiO2@TAPT-DMTP-COF]]> 3.16 22.75 2.85

[0043] As Figure 3 shown, TAPT-DMTP COF has a strong diffraction peak at 2.74°, and relatively weak peaks appear at 4.73°, 5.47°, 7.26° and 25.60°, corresponding to the (100), (110), (200), (210), (101) crystal planes of the P6 / m space group respectively. By comparing the XRD curves of the SiO2-GTPS and SiO2@TAPT-DMTP stationary phases, it can be seen that after grafting SiO2-GTPS with TAPT-DMTP COF, the prepared SiO2@TAPT-DMTP stationary phase shows a characteristic diffraction peak of TAPT-DMTP COF at 2.74°, which proves the successful synthesis of this stationary phase.

[0044] As Figure 4 shown, it can be clearly seen from the SEM image that in the SiO2@TAPT-DMTP stationary phase prepared by the room temperature solvothermal method, TAPT-DMTP COF tightly wraps around the spherical SiO2 surface to form a surface morphology similar to "honeycomb".

[0045] TGA was used to study the weight loss of the SiO2-GPTS and SiO2@TAPT-DMTP stationary phases in the temperature range of 30-800 °C. As Figure 5As shown, the weight loss rate of SiO2-GPTS is approximately 9.86%, which is due to the decomposition of the water adsorbed on its surface and the coupling reagent (γ-GLDP) bonded to the surface of SiO2 upon heating. These materials are stable below 300 °C, indicating good thermal stability. At around 350 °C, the weight of SiO2@TAPT-DMTP begins to rapidly decrease, and the surface COFs start to lose weight, and the total weight loss (22.54%) is greater than that of SiO2-GPTS, proving that the TAPT-DMTP COF is successfully bonded to the surface of SiO2-GPTS. The weight loss rate of SiO2-GPTS is approximately 9.86%, which is due to the decomposition of the water adsorbed on its surface and the coupling reagent (γ-GLDP) bonded to the surface of SiO2 upon heating. These materials are stable below 300 °C, indicating good thermal stability. At around 350 °C, the weight of SiO2@TAPT-DMTP begins to rapidly decrease, and the surface COFs start to lose weight, and the total weight loss (22.54%) is greater than that of SiO2-GPTS, proving that the TAPT-DMTP COF is successfully bonded to the surface of SiO2-GPTS.

[0046] Application Example 1:

[0047] A chromatographic column was prepared using Sample 3 obtained in Example 3, and several alkylbenzene isomers were separated in the RPLC mode. Figure 6 The chromatographic separation results are as follows: 1. Toluene; 2. Ethylbenzene; 3. n-Propylbenzene; 4. n-Butylbenzene; 5. n-Pentylbenzene. The results show that the chromatographic column prepared using Sample 3 obtained in Example 3 has good separation performance for alkylbenzenes; chromatographic conditions: mobile phase: ACN:H2O (95:5, v / v); flow rate: 1.0 mL / min; temperature: 25 °C; detection wavelength: 254 nm.

[0048] Application Example 2:

[0049] A chromatographic column was prepared using Sample 3 obtained in Example 3, and several aniline compounds were separated in the RPLC mode. Figure 7 The chromatographic separation results are as follows: 1. p-Phenylenediamine; 2. Aniline; 3. p-Toluidine; 4. m-Nitroaniline; 5. N-Methylaniline. The results show that the chromatographic column prepared using Sample 3 obtained in Example 3 has good separation performance for aniline compounds; chromatographic conditions: ACN:H2O (90:10, v / v); flow rate: 1.0 mL / min; temperature: 25 °C; detection wavelength: 254 nm.

[0050] Application Example 3:

[0051] A chromatographic column was prepared using Sample 3 obtained in Example 3, and the position isomers of chloronitrobenzene were separated in the RPLC mode. Figure 8As its chromatographic separation result, the result shows that the chromatographic column prepared by using Sample 3 obtained in Example 3 has a good separation effect on the position isomers of p-chloronitrobenzene; Chromatographic conditions: mobile phase: ACN:H2O (70:30, v / v); flow rate: 1.0 mL / min; temperature: 25 °C; detection wavelength: 214 nm.

[0052] Application Example 4:

[0053] A chromatographic column was prepared using Sample 3 obtained in Example 3, and the shape-restricted isomers of tocopherol were separated in the RPLC mode. Figure 9 As its chromatographic separation result, the result shows that the chromatographic column prepared by using Sample 3 obtained in Example 3 has a good separation effect on the shape-restricted isomers of tocopherol; Chromatographic conditions: mobile phase: CH3OH:H2O (90:10, v / v); flow rate: 1.0 mL / min; temperature: 10 °C; detection wavelength: 294 nm.

[0054] Application Example 5:

[0055] A chromatographic column was prepared using Sample 3 obtained in Example 3, and several nucleoside / base mixtures were efficiently separated in the HILIC / PALC mode. Figure 10 As its chromatographic separation result, 1-thiourea; 2-cytosine; 3-thymine; 4-adenine; 5-inosine; 6-adenosine; 7-guanosine. The result shows that the chromatographic column prepared by using Sample 3 obtained in Example 3 has a good separation effect on the nucleoside / base mixture; Chromatographic conditions: mobile phase: ACN:H2O; flow rate: 1.0 mL / min; temperature: 25 °C; detection wavelength: 254 nm.

[0056] It should be noted that: for those of ordinary skill in the art of this technology, without departing from the principles and purposes of the present invention, several improvements, substitutions, variations and refinements can still be made, and these improvements, substitutions, variations and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A novel honeycomb-like COF-functionalized silica-based chromatographic stationary phase, characterized in that, The honeycomb-like novel COF-functionalized silica-based chromatographic stationary phase uses silica gel as the matrix, and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) as raw materials. Through the Schiff base aldehyde-amine condensation reaction, two-dimensional covalent organic framework (COF) is in-situ grown on the silica gel to form the honeycomb-like novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF. The structure of the honeycomb-like novel SiO2@TAPT-DMTP-COF chromatographic stationary phase is as follows:

2. The novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase according to claim 1, wherein The silica gel matrix is spherical, with a particle size of 5 - 6 μm, a pore size of 8 - 15 nm, and a specific surface area of 300 m 2 g -1 .

3. A novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase as claimed in claim 1, wherein, The dosage of TAPT-DMTP-COF contained in each gram of the silica gel matrix is 0.2 - 1.5 g.

4. The novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase according to claim 1, wherein, The COF contains a covalent triazine structure, and TAPT-DMTP-COF self-assembles and grows on the silica gel surface to form a dense honeycomb-like porous structure coating layer.

5. A preparation method of a novel honeycomb-like COF-functionalized silica-based chromatographic stationary phase, characterized in that, The specific method is as follows: Step 1: Silica gel activation: According to a certain mass ratio, disperse the unactivated silica gel particles in hydrochloric acid solution, heat and stir under reflux for 7 - 9 h, cool to room temperature, wash by centrifugation with deionized water for multiple times, and then dry at 120 - 130 °C for 12 - 24 h; Step 2: Preparation of silane coupling agent-modified SiO2: According to a certain ratio, disperse the activated spherical silica gel particles in anhydrous toluene, add a silane coupling agent, reflux and stir in a nitrogen atmosphere for 12 - 24 h, then cool to room temperature, filter, and wash 3 times with toluene, ethanol, and acetone in sequence, and dry at 60 - 100 °C for 12 - 24 h to obtain modified SiO2. The silane coupling agent has γ-glycidoxypropyl. Step 3: Synthesis of SiO2@TAPT-DMTP-COF chromatographic stationary phase: Disperse 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde in an acetonitrile solution according to a certain molar ratio; successively add the modified SiO2 and acetic acid, and let it stand at room temperature for 24 - 72 h; after standing, wash by centrifugation with tetrahydrofuran and ethanol in sequence, and dry at 65 - 75 °C for 12 - 16 h to obtain the honeycomb-like novel COF-functionalized silica-based chromatographic stationary phase SiO2@TAPT-DMTP-COF.

6. The preparation method of a novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase according to claim 5, characterized in that, It is characterized in that In Step 1, the concentration of hydrochloric acid for activating silica gel is 3 mol / L; the temperature of heating under reflux is 100 - 120 °C.

7. The preparation method of a novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase according to claim 5, characterized in that, In Step 2, the ratio of activated silica gel, anhydrous toluene, and silane coupling agent is 1 g:(10 - 20) mL:(3 - 4) mL. The silane coupling agent with γ-glycidoxypropyl is γ-glycidoxypropyltrimethoxysilane.

8. The preparation method of a novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase according to claim 5, characterized in that, In Step 3, the molar ratio of TAPT to DMTP is (0.035 - 0.055) mmol:(0.070 - 0.10) mmol, and the addition ratio of acetonitrile, acetic acid, and SiO2-GPTS is (5.0 - 7.0) mL:(0.50 - 0.65) mL:(30.0 - 50.0) mg; the concentration of acetic acid is 4 - 7 mol / L.

9. Application of a novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase, characterized in that, The novel COF-functionalized silica-based chromatographic stationary phase with a honeycomb morphology is used for separating hydrophobic compounds, polar compounds, shape-restricted isomers, and positional isomers in the reversed-phase chromatography mode under the HPLC mode, and for separating nucleoside and nucleobase compounds in the HILIC and PALC modes.

10. Use of a novel honeycomb-shaped COF-functionalized silica-based chromatographic stationary phase as described in claim 9, characterized in that, The hydrophobic compounds are alkylbenzenes; the polar compounds are aniline-based analytes; the shape-restricted isomers include polycyclic aromatic hydrocarbons, tocopherol isomers, and carotenoid isomers; the positional isomers include xylene, dichlorobenzene, nitroaniline, and chloronitrobenzene.

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