CN115582144A - Hierarchical pore covalent organic framework-metal composite structure catalyst and preparation method and application thereof - Google Patents

Hierarchical pore covalent organic framework-metal composite structure catalyst and preparation method and application thereof Download PDF

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CN115582144A
CN115582144A CN202211054657.7A CN202211054657A CN115582144A CN 115582144 A CN115582144 A CN 115582144A CN 202211054657 A CN202211054657 A CN 202211054657A CN 115582144 A CN115582144 A CN 115582144A
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CN115582144B (en
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彭永武
李南均
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Zhejiang University of Technology ZJUT
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
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Abstract

The invention discloses a hierarchical pore covalent organic framework-metal composite structure catalyst, a preparation method and application thereof, wherein the hierarchical pore catalyst mainly comprises metal active species and a carrier of the covalent organic framework with the hierarchical pore structure, wherein the metal active species accounts for 0.1-40% of the weight of the catalyst; the preparation method comprises the following steps: preparing a polystyrene array material; (2) Preparing a hierarchical porous covalent organic framework material by taking a polystyrene array material as a template; (3) Carrying the metal active species on a multi-stage Kong Youji frame carrier in situ by using a normal-temperature solution impregnation method to obtain a target catalyst; the catalyst can be used for aqueous phase Suzuki-Miyaura reaction, shows catalytic activity as low as room temperature, excellent catalytic selectivity and stability, can realize multiple-batch application, is convenient for aftertreatment, and is green and environment-friendly.

Description

Hierarchical pore covalent organic framework-metal composite structure catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material preparation and catalysis, and particularly relates to a multi-level pore covalent organic framework-metal composite structure porous catalyst, a water phase preparation method thereof, and application of the multi-level pore covalent organic framework-metal composite structure porous catalyst in preparation of biphenyl compounds by water phase catalysis of Suzuki-Miyaura cross-coupling reaction.
Background
Biphenyl compounds are important framework molecules of many important agricultural bactericides, such as boscalid, fluxapyroxad and bixafen, and Suzuki-Miyaura cross-coupling reaction of aryl chloride and aryl boric acid compounds under the catalysis of palladium is an effective method for preparing the biphenyl compounds, but the reaction has the defects of low reaction yield, large using amount of noble metal catalysts, use of organic solvents and the like, which cause the problems of production cost, pollution and the like (J.Am.chem.Soc., 2012,134,3190-3198 org.Process Res.Dev.,2020,24,101-105 Green Chem.,2021,23,8169-8180. Therefore, the development of green catalysts and catalytic systems applicable to Suzuki-Miyaura cross-coupling reactions is essential for the preparation of these biphenyl compounds.
Covalent Organic Frameworks (COFs), also known as organic zeolites, are a class of novel porous organic crystalline materials with periodic pore structures formed by covalently linking organic building units. Different from the traditional amorphous carbon material, the COFs material is prepared by utilizing a dynamic covalent chemical method, so that covalent bonds can be reversibly formed and broken, the defects can be self-repaired, and a long-range ordered porous structure is formed. Ordered pore channels in the COFs material not only can provide a space confinement for a catalytic active site, but also can provide a specific path for the transmission of reaction substrates and products. These characteristics make COFs materials hopeful to be applied to heterogeneous catalytic systems as ideal porous catalytic materials.
Generally, most COFs materials are mainly characterized by pore channels of micropores (< 2 nm), and the more micropores, the larger specific surface area is apparent; the distribution of active sites is facilitated, and the contact between the active sites and a substrate is increased; however, the space between the micropores is relatively long, which is not favorable for the diffusion of the reactant, and thus is not favorable for the reaction in terms of kinetics; relatively speaking, mesopores (2 to 50 nm) are more favorable for the transport of reactants or solvents. Therefore, the construction of COFs materials with hierarchical pores is crucial for their application in the field of heterogeneous catalysis. In addition, the COFs material has the defects of high temperature (120-200 ℃), high pressure sealing, long reaction time (2-7 days), toxic organic solvent, difficulty in large-scale preparation and the like in the traditional preparation process. Therefore, the invention provides a green synthesis method for preparing COFs materials in an aqueous solution of acetic acid or p-toluenesulfonic acid by using polystyrene as a template at room temperature. The method has the advantages of short reaction time, no use of toxic organic solvents and the like, and is suitable for large-scale green preparation of COFs materials.
Based on the background, the invention takes a multi-level pore functionalized Covalent Organic Frameworks (COFs) material as a carrier, and takes the advantages of designable, adjustable and modifiable ordered nano-pore channels, high stability and the like of the structure of the COFs material as a basis, and prepares the porous catalyst with the multi-level pore covalent organic frameworks-metal composite structure in situ based on the principle of metal organic chemistry, and the prepared porous catalyst shows excellent catalytic activity in the preparation of the biphenyl compound by the water-phase Suzuki-Miyaura cross-coupling reaction.
Disclosure of Invention
Aiming at the problems of large catalyst dosage, high cost, organic solvent system pollution and the like in the Suzuki-Miyaura cross-coupling reaction under the catalysis of the existing palladium, the invention provides a porous catalyst with a multi-level pore covalent organic framework-metal composite structure, a green preparation method of the porous catalyst by using an aqueous phase template method, and application of the porous catalyst in the Suzuki-Miyaura cross-coupling reaction of efficiently catalyzing aryl chloride and aryl boric acid compounds under the condition of aqueous phase low metal loading.
The porous catalyst with the hierarchical pore covalent organic framework-metal composite structure is prepared by preparing the hierarchical pore covalent organic framework material by a normal-temperature water-phase template method and further loading metal in the ordered pores of the hierarchical pore covalent organic framework by a normal-temperature dipping in-situ reaction method. The catalyst shows excellent Suzuki-Miyaura cross-coupling catalytic activity in a normal-temperature aqueous phase under low metal loading, not only avoids the influence of the use of an organic solvent on the environment, but also can realize multi-batch application, and is convenient for post-treatment and environment-friendly.
The technical scheme of the invention is as follows:
a preparation method of a hierarchical pore covalent organic framework-metal composite structure catalyst comprises the following steps:
(1) Styrene, PVP and K 2 S 2 O 8 Reacting in solvent water at 50-70 deg.c (preferably 60 deg.c) for 3-5 hr (preferably 4 hr)Then cooling to room temperature, and centrifugally washing to obtain a polystyrene array material;
the styrene, PVP and K 2 S 2 O 8 The mass ratio of (1): 0.03-0.05: 0.01 to 0.02;
(2) Ultrasonically mixing and dispersing the precursor A and the precursor B in an acetic acid or p-toluenesulfonic acid aqueous solution of a polystyrene array material, placing a reaction system at room temperature for reacting for 24-168 hours, and then carrying out post-treatment to obtain a hierarchical porous covalent organic framework material;
the molar ratio of the precursor A to the precursor B is 1:1 to 3, preferably 1:1.5;
the concentration of the acetic acid or p-toluenesulfonic acid aqueous solution is 0.5-9M, wherein the mass fraction of the polystyrene array material is 4-6%;
the volume mol ratio of the acetic acid or p-toluenesulfonic acid water solution to the precursor A is 10-50: 1mL/mmol, preferably 25:1mL/mmol;
the post-treatment method comprises the following steps: after the reaction is finished, filtering the reaction solution, washing the filtered crude product with hot water, dichloromethane and tetrahydrofuran respectively, then carrying out Soxhlet extraction in the tetrahydrofuran, and finally carrying out vacuum drying at 80-120 ℃ for 24h to obtain the hierarchical porous covalent organic framework material;
(3) Uniformly mixing an alkaline substance and a metal precursor in a solvent, adding a multi-level pore covalent organic framework material, soaking for 1-3 h, then putting a reaction system into 77K liquid nitrogen for cooling, freeze thawing and degassing, sealing, then reacting for 1-72 h in a dark place at 50-80 ℃, and then carrying out post-treatment to obtain the multi-level pore covalent organic framework-metal composite structure catalyst;
the basic substance is potassium hydroxide (in the form of an aqueous/alcoholic solution), sodium hydroxide (in the form of an aqueous/alcoholic solution), ammonia (in the form of an aqueous/alcoholic solution), triethylamine, diisopropylamine, sodium tert-butoxide or potassium tert-butoxide; the quantity ratio of the alkaline substance to the substance of the multi-level hole covalent organic framework material is 0.1-10: 1;
the solvent is at least one of acetone, tetrahydrofuran, ethanol, methanol, chloroform, dioxane and dichloromethane; the volume mass ratio of the solvent to the multi-level hole covalent organic framework material is 1-10: 1mL/g;
the metal element in the metal precursor is one or more of zinc, cobalt, nickel, copper, manganese, cadmium, vanadium, iron, silver, palladium, platinum, gold, ruthenium, rhenium, molybdenum, iridium and tin, and palladium is preferred; the metal element has a positive valence metal (monovalent, divalent or trivalent) property;
preferably, the metal precursor is one or more of palladium (II) acetate, palladium (II) chloride, palladium (II) acetylacetonate, palladium (II) nitrate, bis (acetonitrile) palladium (II) chloride, tetrakis (acetonitrile) palladium (II) bis (trifluoromethanesulfonic acid), palladium (II) tetranitrile tetrafluoroborate, bis (acetonitrile) palladium (II) p-toluenesulfonate, and particularly preferably palladium (II) acetate;
the mass ratio of the metal precursor to the hierarchical porous covalent organic framework material is 1:0.1 to 10;
the post-treatment method comprises the following steps: after the reaction is finished, centrifuging the reaction solution, centrifuging and filtering the solid product by using acetone, drying in the dark place, and drying in the dark place at normal temperature in vacuum to obtain the hierarchical porous covalent organic framework-metal composite structure catalyst; in the obtained catalyst, the loading amount of the metal active component is 0.1-40%;
in the step (2), the precursor a is one or more of aldehyde precursors, and the aldehyde precursors have the following structural formula:
Figure BDA0003824534540000021
the precursor B is one or more of an amine precursor and a hydrazide precursor, and the structural formulas of the amine precursor and the hydrazide precursor are as follows:
Figure BDA0003824534540000031
the "precursor a" and "precursor B" have no special meaning, and the labels "a" and "B" are only used to distinguish different kinds of precursors.
The preparation principle of the hierarchical pore covalent organic framework-metal composite structure catalyst is as follows:
the preparation method comprises the steps of preparing a hierarchical porous covalent organic framework with functional groups as a carrier at room temperature under a water phase by taking polystyrene as a template, and preparing the hierarchical porous covalent organic framework-metal composite structure catalyst by using a normal-temperature solution impregnation in-situ reaction method. The method utilizes the functionalized group to carry out metal organic reaction with metal, precisely anchors and stabilizes metal active sites, is beneficial to charge transfer between the metal and a valence organic frame, improves the reaction activity of the catalyst and endows the catalyst with the characteristic of normal-temperature catalysis.
The invention also relates to the hierarchical pore covalent organic framework-metal composite structure catalyst prepared by the preparation method. The catalyst can be applied to the preparation of biphenyl compounds by Suzuki-Miyaura cross-coupling reaction of aryl chlorides and aryl boric acid compounds.
Specifically, the application method comprises the following steps:
mixing and dispersing a multi-level pore covalent organic framework-metal composite structure catalyst, substituted phenylboronic acid and substituted chlorobenzene in a solvent, adding an acid-binding agent, reacting at 30-80 ℃, and monitoring by TLC (thin layer chromatography) until the reaction is finished to obtain a biphenyl compound;
the molar ratio of the substituted chlorobenzene to the substituted phenylboronic acid to the acid-binding agent is 1:1 to 1.5:1 to 1.5;
the mass ratio of the multi-level pore covalent organic framework-metal composite structure catalyst to the substituted chlorobenzene is 1:100 to 10000;
the substituted phenylboronic acid is 4-chlorobenzene boric acid, 3,4,5-trifluorobenzene boric acid or 3,4-dichlorobenzene boric acid;
the substituted chlorobenzene is 2-chloronitrobenzene or 2-chloro-4-fluoronitrobenzene;
the acid-binding agent can be inorganic base or organic base; the inorganic base is selected from any one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium phosphate, sodium phosphate and lithium hydroxide, preferably sodium carbonate or potassium phosphate; the organic base is selected from any one of triethylamine, pyridine, sodium methoxide, sodium ethoxide, tetrabutyl ammonium hydroxide, alkyl lithium and lithium amide, and triethylamine is preferred;
the solvent may be a protic or aprotic solvent; the protic solvent is selected from methanol, ethanol, propanol, isopropanol or water, preferably water or ethanol; the aprotic solvent is selected from N, N-dimethylformamide, acetone, ethyl acetate, dichloromethane, diethyl ether, carbon tetrachloride, toluene, benzene, N-hexane, cyclohexane, tetrahydrofuran or chloroform, preferably N, N-dimethylformamide.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention combines a functionalized multi-level pore Covalent Organic Framework (COFs), and metal is loaded on the functionalized COFs through reaction, so that the ultrahigh catalytic activity of a metal active site and the excellent characteristics of the COFs, such as high temperature resistance and solvent resistance, are combined together, and a green catalyst for water-phase Suzuki-Miyaura cross-coupling reaction is prepared. In addition, the catalyst is heterogeneous catalysis, can be recycled by filtering and recovering after the reaction is finished, and has the advantages of low cost, environmental friendliness and more green synthesis process compared with the traditional homogeneous catalysis.
The invention not only solves the problems of high catalyst consumption, difficult recovery, low catalyst metal utilization rate and the like of the traditional Suzuki-Miyaura cross-coupling reaction, but also endows the catalyst with the characteristic of normal-temperature catalysis. Compared with the traditional palladium catalyst, the prepared hierarchical pore covalent organic framework-metal composite structure catalyst has the advantages of low catalytic temperature to normal temperature, low cost, high atom utilization rate, high activity and the like. In addition, no porous catalyst capable of catalyzing the Suzuki-Miyaura cross-coupling reaction in a normal-temperature aqueous phase is reported in the current literature and patents.
Drawings
FIG. 1 is a schematic diagram of the synthesis of polystyrene microspheres of example 1.
FIG. 2 is an electron micrograph of the polystyrene microspheres of example 1.
FIG. 3 is a scheme showing the synthesis of the porous covalent organic framework material macro-TpPy of example 2.
FIG. 4 is the experimental and simulated powder diffraction pattern of the porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd prepared in example 3.
FIG. 5 is the scanning electron micrograph (left) and transmission electron micrograph (right) of the porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd prepared in example 3.
FIG. 6 is a schematic diagram of the application of the porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd in the Suzuki-Miyaura cross-coupling reaction in example 4.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided in connection with the specific embodiments to which the invention pertains, and is intended to be illustrative of, but not limiting to.
Example 1: preparation of polystyrene microspheres (PS)
As shown in FIG. 1, 10mL of styrene was washed with 12mL of aqueous NaOH (10 wt%) and deionized water to remove the stabilizer, and then the washed styrene and 0.375g of polyvinylpyrrolidone (PVP, mw-29000) were added to a three-necked round-bottomed flask containing 75mL of water. The mixture was bubbled with nitrogen for 15 minutes, then refluxed at 60 ℃ for 30 minutes under magnetic stirring, and then 12.5mL of a solution containing 0.125g of K 2 S 2 O 8 Was added to the flask to initiate polymerization of styrene. Stirring at 60 ℃: (<500r.p.m.) 4 hours, a milky white dispersion of monodisperse colloidal PS spheres was observed, after which the milky white dispersion was centrifuged, washed with water, and redispersed in 90mL of water, the mass of polymeric microspheres of which was approximately about 5wt%.
Example 2: method for synthesizing hierarchical porous covalent organic framework material macro-TpPy by aqueous phase PS template method
Adding p-toluenesulfonic acid (PTSA, 500mg,2.5 mmol) and 2,5-diaminopyridine dihydrochloride (Py, 82mg, 0.45mmol) into 5mL of the PS (5 wt%) microsphere dispersion prepared above, fully shaking for 10 minutes at room temperature, adding 2,4,6-trihydroxybenzene-1,3,5-trimethylaldehyde (Tp, 63mg, 0.30mmol), shaking at room temperature until the mixture is changed from milky white to orange yellow, pouring the mixture liquid on a clean watch glass, standing overnight at room temperature to dry water, putting the watch glass in an oven at 80 ℃ for reacting for 24 hours, washing the obtained red solid with hot water to remove the excessive p-toluenesulfonic acid, and performing Soxhlet extraction on tetrahydrofuran to remove the PS template, thereby obtaining the multi-porous covalent organic framework material macro-TpPy.
According to the synthesis method, 2,4,6-trihydroxybenzene-1,3,5-trimethylaldehyde is replaced by 1,3,5-tri- (4-formylphenyl) benzene, 1,3,5-tri- (4-formylphenyl) triazine or aldehyde precursors such as mixed aldehyde in a certain proportion, and the aldehyde precursors are assembled with 2,5-diaminopyridine dihydrochloride precursor to obtain other multi-level pore covalent organic framework materials.
According to the synthesis method, 2,5-diaminopyridine dihydrochloride is replaced by amine or hydrazide precursors such as 2,5-diaminopyrazine, 2,5-diaminophthalhydrazide and the like, and the amine or hydrazide precursors are assembled with aldehyde precursors such as 2,4,6-trihydroxybenzene-1,3,5-triformal and the like to obtain other multi-level pore covalent organic framework materials.
Example 3: preparation of hierarchical porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd
Dissolving 26mg of palladium acetate and 0.02mL of diisopropylamine in 2.0mL of acetone, uniformly mixing and standing for 1h, then soaking 20mg of the synthesized hierarchical pore covalent organic framework material macro-TpPy in the solution for activation for 3h, then cooling the reaction system in 77K liquid nitrogen, performing freeze thawing and degassing for three times, and then performing light-shielding impregnation in situ reaction for 72h at 80 ℃. After the reaction, the product is centrifugally filtered by acetone, and the product obtained after the filtration is dried in vacuum at normal temperature in the dark to obtain the hierarchical porous covalent organic framework-composite porous catalyst macro-TpPy @ Pd.
The palladium acetate is replaced by other palladium metal precursors to react with other multi-level pore covalent organic framework materials, and the porous catalyst with other multi-level pore covalent organic framework-palladium composite structures can be obtained by loading according to the method.
According to the synthesis method, the palladium precursor is replaced by one or more of precursors of other metals such as zinc, cobalt, nickel, copper, manganese, cadmium, vanadium, iron, silver, palladium, platinum, gold, ruthenium, rhenium, molybdenum, iridium and tin, so that the porous catalyst with other hierarchical pore covalent organic framework-metal composite structures can be prepared.
Example 4: application of hierarchical porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd in Suzuki-Miyaura cross-coupling reaction
Taking 2.0mg of synthesized hierarchical porous covalent organic frame-palladium composite structure porous catalyst macro-TpPy @ Pd (1 mol%), mixing with sodium carbonate (53mg, 0.5mmol), 2-chloronitrobenzene (79mg, 0.5mmol) and 3,4,5-trifluorophenylboronic acid (97mg, 0.55mmol), adding 1mL of water, reacting at 30 ℃ for 3h, and performing post-treatment to obtain 3,4,5-trifluoro-2' -nitrobiphenyl (124 mg, yield 98%).
Comparative example: (CN 104529786B)
PdCl 2 And adding the 4A molecular sieve into an organic solvent, stirring until the reaction is finished, performing suction filtration, and drying a filter cake to obtain a white powdery solid, namely the Ms-Pd catalyst.
The finished catalyst is used for catalyzing Suzuki-Miyaura cross-coupling reaction of 2-chloronitrobenzene and 3,4,5-trifluorophenylboronic acid, and under the condition that the optimal reaction condition is normal temperature (30 ℃), the acid-binding agent is triethylamine and the reaction solvent is N, N-dimethylformamide, the yield of the finished catalyst reaches 88%.
Compared with a comparative example, the catalyst has the advantages that the catalyst can be catalyzed at normal temperature (30 ℃) and in a water phase system, the catalytic selectivity and the conversion rate are high at the normal temperature, and the catalyst can be recycled and reused. The test conditions in the comparative example are that a normal-temperature organic solvent and triethylamine are used as acid-binding agents, the catalytic activity is low and the environmental pollution is large compared with that of the method, the multi-level pore covalent organic framework material-palladium composite structure porous catalyst is prepared into 3,4,5-trifluoro-2' -nitrobiphenyl through Suzuki-Miyaura cross coupling, the activity and the stability of the catalyst are better, particularly the catalytic conversion conditions are milder, and the circulation stability of the catalyst is better.
Fig. 4 is a test and simulated powder diffraction pattern of the porous covalent organic framework material-palladium composite structure macro-tppy @ pd porous catalyst prepared in example 3, from which it can be seen that the composite structure has bragg peaks at 4.66 °,8.06 °,9.70 ° and 27.22 ° corresponding to (100), (110), (210) and (001) crystal planes, respectively, which indicates that the synthesized porous covalent organic framework material-palladium composite structure macro-tppy @ pd porous catalyst is a high-crystalline two-dimensional layered material.
FIG. 5 is the scanning and transmission electron micrographs of the porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd porous catalyst prepared in example 3, and it can be seen from the scanning and transmission electron micrographs that the porous covalent organic framework material-palladium composite structure macro-TpPy @ Pd porous catalyst prepared has regular multistage Kong Xingmao.
The foregoing detailed description of the preferred embodiments of the invention. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Experiments and technical solutions which can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments on the basis of the prior art according to the concept of the present invention are within the scope of protection defined by the appended claims.

Claims (10)

1. A preparation method of a hierarchical pore covalent organic framework-metal composite structure catalyst is characterized by comprising the following steps:
(1) Styrene, PVP and K 2 S 2 O 8 Reacting in solvent water at 50-70 ℃ for 3-5 h, cooling to room temperature, and centrifugally washing to obtain the polystyrene array material;
(2) Ultrasonically mixing and dispersing the precursor A and the precursor B in an acetic acid or p-toluenesulfonic acid aqueous solution of a polystyrene array material, placing a reaction system at room temperature for reacting for 24-168 hours, and then carrying out post-treatment to obtain a hierarchical porous covalent organic framework material;
(3) Uniformly mixing an alkaline substance and a metal precursor in a solvent, adding a multi-level pore covalent organic framework material, soaking for 1-3 h, then putting a reaction system into 77K liquid nitrogen for cooling, freeze thawing and degassing, sealing, then reacting for 1-72 h in a dark place at 50-80 ℃, and then carrying out post-treatment to obtain the multi-level pore covalent organic framework-metal composite structure catalyst;
the metal element in the metal precursor is one or more of zinc, cobalt, nickel, copper, manganese, cadmium, vanadium, iron, silver, palladium, platinum, gold, ruthenium, rhenium, molybdenum, iridium and tin;
in the step (2), the precursor a is one or more of aldehyde precursors, and the aldehyde precursors have the following structural formula:
Figure FDA0003824534530000011
r = H, X (halogen), OH, CN, OCH 3 ；
The precursor B is one or more of an amine precursor and a hydrazide precursor, and the structural formulas of the amine precursor and the hydrazide precursor are as follows:
Figure FDA0003824534530000012
2. the method of claim 1, wherein in step (1), the styrene, PVP and K are mixed together to form the multi-stage porous covalent organic framework-metal composite catalyst 2 S 2 O 8 The mass ratio of (1): 0.03 to 0.05:0.01 to 0.02.
3. The method for preparing the hierarchical porous covalent organic framework-metal composite structure catalyst according to claim 1, wherein in the step (2), the molar ratio of the precursor A to the precursor B is 1:1 to 3.
4. The preparation method of the hierarchical porous covalent organic framework-metal composite structure catalyst according to claim 1, wherein in the step (2), the concentration of the acetic acid or p-toluenesulfonic acid aqueous solution is 0.5-9M, wherein the mass fraction of the polystyrene array material is 4-6%; the volume mol ratio of the acetic acid or p-toluenesulfonic acid water solution to the precursor A is 10-50: 1mL/mmol.
5. The method for preparing the hierarchical porous covalent organic framework-metal composite structure catalyst according to claim 1, wherein in the step (3), the basic substance is potassium hydroxide, sodium hydroxide, ammonia, triethylamine, diisopropylamine, sodium tert-butoxide or potassium tert-butoxide; the quantity ratio of the alkaline substance to the substance of the multi-level hole covalent organic framework material is 0.1-10: 1.
6. the method for preparing the hierarchical porous covalent organic framework-metal composite structure catalyst according to claim 1, wherein in the step (3), the solvent is at least one of acetone, tetrahydrofuran, ethanol, methanol, chloroform, dioxane and dichloromethane; the volume mass ratio of the solvent to the multi-level hole covalent organic framework material is 1-10: 1mL/g.
7. The method for preparing the multi-stage pore covalent organic framework-metal composite structure catalyst according to claim 1, wherein in the step (3), the metal precursor is one or more of palladium (II) acetate, palladium (II) chloride, palladium (II) acetylacetonate, palladium (II) nitrate, bis (acetonitrile) palladium (II) chloride, tetrakis (acetonitrile) palladium (II) bis (trifluoromethanesulfonic acid), tetraacetonitrile palladium (II) tetrafluoroborate, bis (acetonitrile) palladium (II) p-toluenesulfonate; the mass ratio of the metal precursor to the hierarchical porous covalent organic framework material is 1:0.1 to 10.
8. The hierarchical porous covalent organic framework-metal composite structure catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the multi-staged pore covalent organic framework-metal composite structure catalyst of claim 8 in the preparation of biphenyl compounds by Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acid compounds.
10. The application of claim 9, wherein the method of applying is:
mixing and dispersing a multi-level pore covalent organic framework-metal composite structure catalyst, substituted phenylboronic acid and substituted chlorobenzene in a solvent, adding an acid-binding agent, reacting at 30-80 ℃, and monitoring by TLC (thin layer chromatography) until the reaction is finished to obtain a biphenyl compound;
the molar ratio of the substituted chlorobenzene to the substituted phenylboronic acid to the acid-binding agent is 1:1 to 1.5:1 to 1.5;
the mass ratio of the multi-level pore covalent organic framework-metal composite structure catalyst to the substituted chlorobenzene is 1:100 to 10000;
the substituted phenylboronic acid is 4-chlorobenzene boric acid, 3,4,5-trifluorobenzene boric acid or 3,4-dichlorobenzene boric acid;
the substituted chlorobenzene is 2-chloronitrobenzene or 2-chloro-4-fluoronitrobenzene;
the acid-binding agent is inorganic base or organic base;
the solvent is a protic solvent or an aprotic solvent.
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