COF composite material and preparation method and application thereof

Abstract

The invention provides a COF composite material as well as a preparation method and application thereof, and relates to the technical field of heterogeneous catalysis. The preparation method provided by the invention comprises the following steps: in an inert atmosphere and a solvent environment, mixing a P-COF material and a ruthenium precursor at 30-150 DEG C for reaction, and cooling to obtain an intermediate; mixing and reacting the intermediate with an SNS ligand at 20-110 DEG C, and then separating and drying to obtain the COF composite material. As a catalyst, the COF composite material provided by the invention can be applied to catalytic hydrogenation reaction of unsaturated organic matters containing C = C, C = C, C = O bonds and the like. In addition, the catalyst provided by the invention is easy to separate from a reaction product, and has good recycling performance.

Description

Technical Field

[0001] The present invention relates to the technical field of heterogeneous catalysis, and in particular to a COF composite material and a preparation method and application thereof. Background Art

[0002] Hydrogenation reduction is a common organic reaction. Saturated organic matter can be generated by catalytic oxidation of unsaturated C=X bonds. Compared with other processes, no by-products are produced, which has obvious advantages in both the environment and the economy. For example, under relatively mild conditions, PNN-type ruthenium hydrogenation complexes and PNP-type ruthenium hydrogenation complexes are used as hydrogenation catalysts to hydrogenate aromatic esters and aliphatic esters to the corresponding alcohols. In addition, there are SNS-type clamp-type ruthenium complex hydrogenation catalysts, which have shown excellent efficiency in the hydrogenation reduction of a wide range of substrates (esters, ketones, and imines) with C=X bonds. However, although the homogeneous catalytic system commonly used in the prior art has excellent catalytic activity for the hydrogenation of unsaturated substrates, the homogeneous catalyst will remain in the reaction system, resulting in difficulty in separating the catalyst from the product, and the catalyst is difficult to reuse. Therefore, it is urgent to provide a solution to improve the above problems. Summary of the invention

[0003] The purpose of the present invention is to illustrate a preparation method and application of a COF composite material. The COF composite material is used as a catalyst, is easy to separate from the reaction product, and has good recycling performance.

[0004] In the first aspect, the present invention provides a method for preparing a COF composite material. In an inert atmosphere and solvent environment, a P-COF material and a ruthenium precursor are mixed and reacted at 30-150°C and then cooled to obtain an intermediate; the intermediate is mixed and reacted with a SNS ligand at 20-110°C and then separated and dried to obtain a COF composite material.

[0005] The present invention uses the P-COF material as an active carrier to increase the catalytic contact area, thereby enhancing the catalytic performance, and can effectively limit the movement of the active center, making it difficult to lose or aggregate into clusters. At the same time, it can also make the overall catalytic reaction into a heterogeneous reaction, which is easy to separate and recover after the reaction, so that the composite material can be recycled. In addition, the SNS ligand still retains the NH structure, which can provide an electron-rich coordination environment for the active center, and can use the synergistic catalytic effect of metal / ligand.

[0006] Optionally, the molar ratio of the phosphorus sites in the P-COF material to the ruthenium element in the ruthenium precursor is (1-100):1.

[0007] Optionally, the molar ratio of phosphorus sites in the P-COF material to ruthenium elements in the ruthenium precursor is (1-20):1.

[0008] Optionally, the molar ratio of the SNS ligand to the ruthenium precursor is (0.5-2):1.

[0009] Optionally, the molar ratio of the SNS ligand to the ruthenium precursor is (1-1.5):1.

[0010] Optionally, the ruthenium precursor includes at least one of bis(phenylruthenium dichloride), dichloro(pod)ruthenium(II) dimer, isopropylphenylruthenium dichloride, dichloro(p-methylisopropylbenzene)ruthenium dimer, cyclooctadieneruthenium dichloride, tricarbonyldichlororuthenium dimer, hexaammineruthenium(II) chloride, diiodo(p-cymene)ruthenium(II) dimer, bis(ethylcyclopentadiene)ruthenium(II), and dichlorotetrakis(triphenylphosphine)ruthenium;.

[0011] Optionally, the solvent environment includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, n-hexane, heptane, octane, 1,4-dioxane, and tetrahydrofuran. Preferably, the solvent environment is at least one of toluene, tetrahydrofuran, and 1,4-dioxane.

[0012] Optionally, the inert atmosphere includes at least one of an argon atmosphere and a nitrogen atmosphere.

[0013] Optionally, the P-COF material and the ruthenium precursor are mixed and reacted at 60-120°C.

[0014] Optionally, the P-COF material is mixed with a ruthenium precursor and reacted for 5-12 hours.

[0015] Optionally, the intermediate and the SNS ligand are mixed and reacted at 20-120°C.

[0016] Optionally, the intermediate is mixed with the SNS ligand for reaction for 5-12 hours.

[0017] Optionally, the method comprises the following steps: under an inert atmosphere, mixing a P-COF material and a ruthenium precursor and dispersing them in a solvent environment, stirring and reacting them at 30-150° C. for 1-72 hours, and then cooling to obtain an intermediate; maintaining the atmosphere, adding an SNS-type ligand to the intermediate, stirring and reacting them at 20-110° C. for 1-72 hours, and then separating, washing and drying to obtain a COF composite material.

[0018] In a second aspect, the present invention further provides a COF composite material prepared by any of the above optional preparation methods.

[0019] Optionally, the structure of the COF composite material is as shown in Formula I:

[0020]

[0021] The L1 and L 2 are independently hydrogen, halogen, cyano, C1-C5 alkyl, aryl;

[0022] The Ar 1 and the Ar 2 are independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl;

[0023] The R 1 , R 2 , R 5 , R 6 are independently hydrogen, C1-C 10 Linear or branched alkyl, C3-C8 cyclic alkyl and C5-C 10 One of the aryl groups, or, the R 1 With the R 2 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 5 and the R 6 forming a saturated or unsaturated, substituted or unsubstituted aromatic ring;

[0024] The R 3 , R 4 are independently hydrogen, C1-C8 linear or branched alkyl, C4-C 10 A cyclic alkyl group or a cyclic alkenyl group, a C5-C8 aryl group or an ester group, or, said R 3 and the R 4 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 2 and the R 3 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 4 and R 5 forming a saturated or unsaturated, substituted or unsubstituted aromatic ring;

[0025] The m and n are independently one of 0, 1, and 2.

[0026] In a third aspect, the present invention also provides related applications of a COF composite material catalyst prepared according to the above preparation method.

[0027] Optionally, the application includes catalyzing as a catalyst in a hydrogenation reaction of an unsaturated organic matter, wherein the unsaturated organic matter has at least one unsaturated bond, and the unsaturated bond includes a C═C, C≡C, or C═O bond.

[0028] Optionally, the application includes hydrogenating unsaturated organic matter having a molar mass less than or equal to 300 g / mol under the catalysis of the COF composite material in a hydrogen atmosphere at 40-200° C. and an alkaline solvent environment.

[0029] Optionally, the unsaturated organic matter is subjected to a hydrogenation reaction in a hydrogen atmosphere at 60-160°C.

[0030] Optionally, the unsaturated organic matter is reacted under a hydrogen atmosphere for 1-72 hours.

[0031] Optionally, the unsaturated organic matter is subjected to a hydrogenation reaction in a hydrogen atmosphere of 0.5-6 MPa.

[0032] Optionally, the alkaline solute in the alkaline solvent environment includes at least one of potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, sodium methoxide, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium carbonate, and sodium bicarbonate.

[0033] Optionally, the solvent in the alkaline solvent environment includes one of benzene, toluene, xylene, anisole, tetrahydrofuran, and 1,4-dioxane.

[0034] Optionally, the unsaturated organic matter includes but is not limited to at least one of acetophenone, p-phenoxyacetophenone, p-methylacetophenone, p-chloroacetophenone, p-bromoacetophenone, p-nitroacetophenone, 4-biphenylacetophenone, acetone, cyclohexanone, benzaldehyde, furfural, 2-naphthaldehyde, p-hydroxybenzaldehyde, vanillin, salicylaldehyde, 5-(hydroxymethyl)furfural, terephthalaldehyde, 3,4-dimethoxybenzaldehyde, 5-bromofuran-2-carboxaldehyde, cyclohexene, styrene, m-chlorostyrene, phenylacetylene, m-tolueneacetylene, p-chlorophenylacetylene, methyl benzoate, ethyl benzoate, valerolactone, and caprolactone. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 A flow chart of a method for preparing a COF composite material provided in an embodiment of the present invention;

[0036] Figure 2 A structural formula of a COF composite material is provided for an embodiment of the present invention;

[0037] Figure 3 This is a nuclear magnetic hydrogen spectrum characterization diagram of the reactant prepared in Application Example 1 of the present invention;

[0038] Figure 4 This is the nuclear magnetic hydrogen spectrum characterization diagram of the reactant prepared in Application Example 2 of the present invention. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with general skills in the field to which the present invention belongs.

[0040] An embodiment of the present invention provides a method for preparing a COF composite material, wherein a P-COF material and a ruthenium precursor are mixed and reacted at 30-150° C. in an inert atmosphere and a solvent environment, followed by cooling to obtain an intermediate; and the intermediate is mixed and reacted with an SNS ligand at 20-110° C., followed by separation and drying to obtain a COF composite material.

[0041] In fact, due to the advantages of COF materials such as orderly pore structure, adjustable pore size, large specific surface area, diverse synthesis methods and easy surface functionalization modification, they can be well used as catalyst supports. P-COF materials are COF materials formed by cross-linking with phosphorus-containing aromatic groups as the basic structure.

[0042] In fact, by using P-COF materials as active carriers, the catalytic contact area can be increased, thereby enhancing the catalytic properties. In addition, P-COF materials can also effectively limit the movement of active centers, making them less likely to be lost or aggregated into clusters. At the same time, they can also make the overall catalytic reaction a heterogeneous reaction, which is easy to separate and recover after the reaction, so that the composite material can be recycled. In addition, the SNS ligand still retains the NH structure, which can provide an electron-rich coordination environment for the active center, and can use the synergistic catalytic effect of metal / ligand.

[0043] In some embodiments, the structure of the P-COF material is shown in Formula II:

[0044]

[0045] Among them, Ar 1 and Ar 2 Independently of each other, they are substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted biphenyl, and substituted or unsubstituted terphenyl. In fact, the part connected to P in the P-COF material can be continuously extended outward to form a continuous porous structure.

[0046] In fact, the P-COF material shown in Formula II can not only serve as a carrier to load the active ingredients, but also play the role of a partial ligand. It has a specific pore structure, specific surface area, pore size distribution and good thermal stability.

[0047] Specifically, in an inert atmosphere solvent environment, reacting the P-COF material with the ruthenium precursor under a heating environment can promote the loading of the P-COF material on the ruthenium precursor and improve the loading uniformity. In fact, when reacting the P-COF material with the ruthenium precursor, mechanical stirring, ultrasonic mixing, and physical shaking can be used to uniformly mix them.

[0048] In fact, when the intermediate is mixed with the SNS ligand for reaction, the SNS ligand participates in the coordination of ruthenium at three sites: S, N, and S, and also has an NH bond. After completing the coordination with ruthenium, a pincer-type organic metal complex is formed. In addition, the addition of the SNS ligand can significantly improve the catalytic activity of the COF composite material.

[0049] In some embodiments, when the P-COF material and the ruthenium precursor are mixed and reacted, the molar ratio of the phosphorus site in the P-COF material to the ruthenium element in the ruthenium precursor is (1-100):1. In fact, during the mixed reaction, the phosphorus site in the P-COF material can coordinate with ruthenium, so that by adjusting the amount of ruthenium added, the loading amount of ruthenium and the coordination amount of ruthenium in the P-COF material can be effectively controlled. Preferably, the molar ratio of the phosphorus site in the P-COF material to the ruthenium element in the ruthenium precursor is (1-20):1.

[0050] In fact, the ruthenium precursor includes at least one of bis(phenyl dichloride), dichloro(pod)ruthenium(II) dimer, isopropylphenyl dichloride, dichloro(p-methylisopropylbenzene)ruthenium dimer, cyclooctadiene dichloride, tricarbonyl dichlororuthenium dimer, hexaammine chlorinated ruthenium(II), diiodo(p-cymene)ruthenium(II) dimer, bis(ethylcyclopentadiene)ruthenium(II), and dichlorotetrakis(triphenylphosphine)ruthenium. Specifically, the ruthenium precursor is added to the solvent environment, and the divalent ruthenium can be well attached to the P-COF material to form an intermediate.

[0051] Specifically, the solvent environment includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, n-hexane, heptane, octane, 1,4-dioxane, and tetrahydrofuran, and preferably the solvent environment is at least one of toluene, tetrahydrofuran, and 1,4-dioxane. Specifically, the inert atmosphere includes at least one of an argon atmosphere and a nitrogen atmosphere.

[0052] In some embodiments, the P-COF material and the ruthenium precursor are mixed and reacted at 60-120° C. Specifically, the P-COF material and the ruthenium precursor are mixed and reacted for 5-12 hours.

[0053] In some embodiments, when the intermediate is mixed with the SNS ligand for reaction, the molar ratio of the SNS ligand to the ruthenium precursor is (0.5-2):1, which is conducive to the coordination of the SNS ligand with ruthenium to form a pincer complex, thereby synergistically improving the hydrogenation catalytic activity of the composite material with the ruthenium element. Preferably, the molar ratio of the SNS ligand to the ruthenium precursor is (1-1.5):1.

[0054] In practice, the intermediate and the SNS ligand are mixed and reacted at 20-120° C., and specifically, the intermediate and the SNS ligand can be mixed and reacted for 5-12 hours.

[0055] In some embodiments, see Figure 1 The preparation method of the COF composite material provided by the present invention comprises the following steps:

[0056] S1. Under an inert atmosphere, the P-COF material and the ruthenium precursor are mixed and dispersed in a solvent environment, and stirred at 30-150° C. for 1-72 hours and then cooled to obtain an intermediate;

[0057] S2. Maintaining the atmosphere, adding the SNS type ligand to the intermediate, stirring and reacting at 20-110° C. for 1-72 hours, separating, washing and drying to obtain the COF composite material.

[0058] In fact, see Figure 2 The present invention also provides a COF composite material, which is prepared by the preparation method in any of the above optional embodiments, and its structure is shown in Formula I:

[0059]

[0060] Among them, L 1 and L 2 are independently hydrogen, halogen, cyano, C 1- C5 alkyl, aryl; Ar 1 and Ar 2 are independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted biphenyl, or substituted or unsubstituted terphenyl; R 1 , R 2 , R 5 , R 6 are independently hydrogen, C1-C 10 Linear or branched alkyl, C3-C8 cyclic alkyl and C5-C 10 One of the aromatic groups, or, R 1 With R 2 constitute a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, R 5 and R 6 Constitute a saturated or unsaturated, substituted or unsubstituted aromatic ring; R 3 , R4 are independently hydrogen, C1-C8 linear or branched alkyl, C4-C 10 A cyclic alkyl group or a cyclic alkenyl group, a C5-C8 aryl group or an ester group, or R 3 and R 4 constitute a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, R 2 and R 3 constitute a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, R 4 and R 5 It constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring; m and n are independently 0, 1, or 2.

[0061] The present invention also provides an application of the COF composite material, for example, as a catalyst in the catalytic hydrogenation reaction of unsaturated organic matter.

[0062] In fact, when the unsaturated organic matter is hydrogenated under the catalytic action of the COF composite material, the reaction conditions are a hydrogen atmosphere at 40-200°C and an alkaline solvent environment. In fact, the unsaturated organic matter has at least one unsaturated bond, including C=C, C≡C, and C=O bonds. Preferably, the unsaturated organic matter is hydrogenated under a hydrogen atmosphere at 60-160°C, and the reaction time is controlled to be 1-72h.

[0063] Specifically, the unsaturated organic matter can be one of acetophenone, p-phenoxyacetophenone, p-methylacetophenone, p-chloroacetophenone, p-bromoacetophenone, p-nitroacetophenone, 4-biphenylacetophenone, acetone, cyclohexanone, benzaldehyde, furfural, 2-naphthaldehyde, p-hydroxybenzaldehyde, vanillin, salicylaldehyde, 5-(hydroxymethyl)furfural, terephthalaldehyde, 3,4-dimethoxybenzaldehyde, 5-bromofuran-2-carboxaldehyde, cyclohexene, styrene, m-chlorostyrene, phenylacetylene, m-tolueneacetylene, p-chlorophenylacetylene, methyl benzoate, ethyl benzoate, valerolactone, and caprolactone.

[0064] In fact, when the unsaturated organic matter is hydrogenated under the catalytic action of the COF composite material, the pressure of the hydrogen atmosphere is 0.5-6MPa. In addition, the alkaline solute in the alkaline solvent environment includes one of potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, sodium methoxide, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium carbonate, and sodium bicarbonate, and the solvent includes one of benzene, toluene, xylene, anisole, tetrahydrofuran, and 1,4-dioxane. Generally, the molar ratio of ruthenium to alkaline solute in the COF composite material is 1:1 to 100.

[0065] Example 1

[0066] Embodiment 1 of the present invention provides a method for preparing a COF composite material, comprising the following steps:

[0067] S1. Under an argon atmosphere, a P-COF material containing 0.25 mmol of phosphorus sites and a ruthenium precursor containing 0.25 mmol of ruthenium element were mixed and dispersed in toluene, and then stirred in an oil bath environment at 100° C. for 6 hours and then cooled to room temperature to obtain an intermediate;

[0068] S2. Under an argon atmosphere, 0.25 mmol of SNS ligand was added to the intermediate, and the mixture was stirred in an oil bath at 100°C for 6 h and then cooled to room temperature. After separation by suction, the solid was washed with toluene and then transferred to a vacuum drying oven at 120°C and dried to constant weight to obtain a COF composite material.

[0069] Example 2

[0070] Embodiment 2 of the present invention provides a method for preparing a COF composite material, comprising the following steps:

[0071] S1. Under an argon atmosphere, a P-COF material containing 0.25 mmol of phosphorus sites and a ruthenium precursor containing 0.13 mmol of ruthenium element were mixed and dispersed in toluene, and then stirred in an oil bath environment at 100° C. for 6 hours and then cooled to room temperature to obtain an intermediate;

[0072] S2. Under an argon atmosphere, 0.25 mmol of SNS ligand was added to the intermediate, and the mixture was stirred in an oil bath at 100°C for 6 h and then cooled to room temperature. After separation by suction, the solid was washed with toluene and then transferred to a vacuum drying oven at 120°C and dried to constant weight to obtain a COF composite material.

[0073] Example 3

[0074] Embodiment 3 of the present invention provides a method for preparing a COF composite material, comprising the following steps:

[0075] S1. Under an argon atmosphere, a P-COF material containing 0.25 mmol of phosphorus sites and a ruthenium precursor containing 0.25 mmol of ruthenium element were mixed and dispersed in toluene, and then stirred in an oil bath environment at 100° C. for 6 hours and then cooled to room temperature to obtain an intermediate;

[0076] S2. Under argon atmosphere, 0.25 mmol of SNS ligand was added to the intermediate, and the reaction was stirred at room temperature of 25°C for 6 hours and then cooled to room temperature. After separation by suction, the solid was washed with toluene and then transferred to a vacuum drying oven at 120°C and dried to constant weight to obtain a COF composite material.

[0077] Application Example 1

[0078] This application example 1 provides a method for catalytic hydrogenation of ethyl benzoate using the COF composite material prepared in application example 1, comprising the following steps:

[0079] Y1. After adding 3.6 mg of COF composite material, 5.6 mg of potassium tert-butoxide, 2 mL of tetrahydrofuran and 150.2 mg of ethyl benzoate into a 25 mL autoclave, the gas in the autoclave was replaced three times with hydrogen, and the hydrogen pressure in the autoclave was adjusted to 4 MPa to obtain a reaction mixture system;

[0080] Y2. After stirring the reaction mixture in a high-pressure reactor at 100° C. for 6 hours, the high-pressure reactor was cooled to room temperature and the COF composite material was recovered by filtration. The NMR yield of benzyl alcohol in the reaction solution was measured to be 91.6%.

[0081] The reactants prepared in Example 1 were characterized by nuclear magnetic resonance spectroscopy. Figure 3 shown.

[0082] Application Example 2

[0083] This application example 2 provides a method for catalytic hydrogenation of furfural using the COF composite material prepared in application example 1, comprising the following steps:

[0084] Y1. After adding 3.6 mg COF composite material, 16.3 mg cesium carbonate, 2 mL tetrahydrofuran, and 96.0 mg furfural into a 25 mL autoclave, the gas in the autoclave was replaced three times with hydrogen, and the hydrogen pressure in the autoclave was adjusted to 4 MPa to obtain a reaction mixture system;

[0085] Y2. After stirring the reaction mixture in a high-pressure reactor at 120° C. for 6 hours, the high-pressure reactor was cooled to room temperature and the COF composite material was recovered by filtration. The NMR yield of furfuryl alcohol in the reaction solution was measured to be ≥99%.

[0086] The reactants prepared in Example 2 were characterized by nuclear magnetic resonance spectroscopy. Figure 4 shown.

[0087] Application Example 3

[0088] This application example 3 provides a method for catalytic hydrogenation of furfural, which is different from application example 2 in that the COF composite material used in step Y1 is a COF composite material recovered after 4 cycles of catalysis, and the nuclear magnetic resonance yield of furfuryl alcohol measured after step Y2 is ≥98%.

[0089] Application Examples 4 to 7

[0090] Application Examples 4 to 7 respectively provide a method for catalytic hydrogenation of unsaturated organic matter using a COF composite material prepared in Application Example 1, which differs from Application Example 2 in the type of base, solvent type and reaction temperature, as shown in Table 1 below.

[0091] Table 1 Base type, solvent type, reaction temperature and yield of Application Examples 4 to 7

[0092]

[0093] Application Example 8 to Application Example 9

[0094] Application Examples 8 to 9 respectively provide a method for catalytic hydrogenation of unsaturated organic matter using the COF composite material prepared in Application Example 1, which differs from Application Example 2 in the type of base, as shown in Table 2 below.

[0095] Table 2 Types and yields of bases in Application Examples 8 to 9

[0096]

[0097] Application Example 10 to Application Example 36

[0098] Application Examples 10 to 36 respectively provide a method for catalytic hydrogenation of unsaturated organic matter using a COF composite material prepared in Application Example 1, which differs from Application Example 6 in the type of unsaturated organic matter, as shown in Table 3 below.

[0099] Table 3 Types and yields of unsaturated organic compounds in Application Examples 10 to 36

[0100]

[0101]

[0102] Application Example 37 to Application Example 40

[0103] Application Examples 37 to 40 respectively provide a method for catalytic hydrogenation of unsaturated organic matter using a COF composite material prepared in Application Example 1, which differs from Application Example 6 in the types of base and unsaturated organic matter, as shown in Table 5 below.

[0104] Table 5 Base types, unsaturated organic types and yields of Application Examples 37 to 40

[0105]

[0106] Although the embodiments of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as described in the claims. Moreover, the present invention described herein may have other embodiments and may be implemented or realized in a variety of ways.

Claims

1. A method for preparing a COF composite material, characterized in that: In an inert atmosphere and solvent environment, the P-COF material and the ruthenium precursor are mixed and reacted at 30-150° C. and then cooled to obtain an intermediate; the intermediate is mixed and reacted with the SNS ligand at 20-110° C. and then separated and dried to obtain a COF composite material.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the phosphorus sites in the P-COF material to the ruthenium element in the ruthenium precursor is (1-100):1, preferably the molar ratio of the phosphorus sites in the P-COF material to the ruthenium element in the ruthenium precursor is (1-20):1; and / or, the molar ratio of the SNS ligand to the ruthenium precursor is (0.5-2):1, preferably the molar ratio of the SNS ligand to the ruthenium precursor is (1-1.5):1; And / or, the ruthenium precursor includes at least one of bis(phenyl ruthenium dichloride), dichloro(pod)ruthenium(II) dimer, isopropylphenyl ruthenium dichloride, dichloro(p-methylisopropylbenzene)ruthenium dimer, cyclooctadiene ruthenium dichloride, tricarbonyl dichlororuthenium dimer, hexaammine ruthenium(II) chloride, diiodo(p-cymene)ruthenium(II) dimer, bis(ethylcyclopentadiene)ruthenium(II), and dichlorotetrakis(triphenylphosphine)ruthenium; And / or, the solvent environment includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, n-hexane, heptane, octane, 1,4-dioxane, and tetrahydrofuran, preferably the solvent environment is at least one of toluene, tetrahydrofuran, and 1,4-dioxane; And / or, the inert atmosphere includes at least one of an argon atmosphere and a nitrogen atmosphere.

3. The preparation method according to claim 1, characterized in that: The P-COF material and the ruthenium precursor are mixed and reacted at 60-120° C.; and / or, the P-COF material is mixed with a ruthenium precursor and reacted for 5-12 hours; and / or, the intermediate and the SNS ligand are mixed and reacted at 20-120° C.; And / or, the intermediate is mixed with the SNS ligand for reaction for 5-12 hours.

4. The preparation method according to claim 1, characterized in that: The following steps are involved: Under an inert atmosphere, the P-COF material and the ruthenium precursor are mixed and dispersed in a solvent environment, and are placed at 30-150°C for stirring and reacting for 1-72 hours, and then cooled to obtain an intermediate; maintaining the atmosphere environment, an SNS-type ligand is added to the intermediate, and the mixture is placed at 20-110°C for stirring and reacting for 1-72 hours, and then separated, washed and dried to obtain a COF composite material.

5. A COF composite material prepared by the preparation method according to any one of claims 1 to 4.

6. The COF composite material according to claim 5, characterized in that: The structure of the COF composite material is shown in Formula I: The L 1 and L 2 are independently hydrogen, halogen, cyano, C1-C5 alkyl, aryl; The Ar 1 and the Ar 2 are independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl; The R 1 , R 2 , R 5 , R 6 are independently hydrogen, C1-C 10 Linear or branched alkyl, C3-C8 cyclic alkyl and C5-C 10 One of the aryl groups, or, the R 1 With the R 2 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 5 and the R 6 forming a saturated or unsaturated, substituted or unsubstituted aromatic ring; The R 3 , R 4 are independently hydrogen, C1-C8 linear or branched alkyl, C4-C 10 A cyclic alkyl group or a cyclic alkenyl group, a C5-C8 aryl group or an ester group, or, said R 3 and the R 4 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 2 and the R 3 constitutes a saturated or unsaturated, substituted or unsubstituted aromatic ring, or, said R 4 and R 5 forming a saturated or unsaturated, substituted or unsubstituted aromatic ring; The m and n are independently one of 0, 1, and 2.

7. A use of the COF composite material prepared by the preparation method according to any one of claims 1 to 4 or the COF composite material according to any one of claims 5 to 6.

8. The use according to claim 7, characterized in that: The application includes being used as a catalyst in a catalytic hydrogenation reaction of unsaturated organic matter, wherein the unsaturated organic matter has at least one unsaturated bond, and the unsaturated bond includes C=C, C≡C, and C=O bonds.

9. The use according to claim 8, characterized in that: The application includes hydrogenation reaction of unsaturated organic matter with a molar mass less than or equal to 300 g / mol under the catalysis of the COF composite material at 40-200° C., hydrogen atmosphere, and alkaline solvent environment.

10. The use according to claim 9, characterized in that: The unsaturated organic matter is subjected to hydrogenation reaction in a hydrogen atmosphere at 60-160°C; and / or, reacting the unsaturated organic matter under a hydrogen atmosphere for 1-72 hours; and / or, subjecting the unsaturated organic matter to a hydrogenation reaction under a hydrogen atmosphere of 0.5-6 MPa; And / or, the alkaline solute in the alkaline solvent environment includes at least one of potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, sodium methoxide, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium carbonate, and sodium bicarbonate; And / or, the solvent in the alkaline solvent environment includes one of benzene, toluene, xylene, anisole, tetrahydrofuran, and 1,4-dioxane; And / or, the unsaturated organic matter includes one of acetophenone, p-phenoxyacetophenone, p-methylacetophenone, p-chloroacetophenone, p-bromoacetophenone, p-nitroacetophenone, 4-biphenylacetophenone, acetone, cyclohexanone, benzaldehyde, furfural, 2-naphthaldehyde, p-hydroxybenzaldehyde, vanillin, salicylaldehyde, 5-(hydroxymethyl)furfural, terephthalaldehyde, 3,4-dimethoxybenzaldehyde, 5-bromofuran-2-carboxaldehyde, cyclohexene, styrene, m-chlorostyrene, phenylacetylene, m-tolueneacetylene, p-chlorophenylacetylene, methyl benzoate, ethyl benzoate, valerolactone, and caprolactone.

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