A metal organic complex supported catalyst, its preparation method and application

Abstract

The application discloses a metal organic complex supported catalyst and a preparation method and application thereof, relates to the technical field of heterogeneous metal organic photocatalyst preparation, and discloses the metal organic complex supported catalyst and the preparation method and application thereof.The preparation method comprises the following steps: mixing hollow mesoporous polystyrene nanometer microspheres, fac-Ir(ppy)3 and DCE, swelling, adding FeCl3, and reacting to prepare HMPNs(S)@Ir, namely the metal organic complex supported catalyst.The fac-Ir(ppy)3 containing a benzene ring is connected with the carbon on the benzyl chloride group in the carrier HMPNs through a one-pot method of Friedel-Crafts alkylation, and the metal organic complex photocatalyst fac-Ir(ppy)3 is anchored in a low-cost mode.The application solves the problem of a complicated modification process of the metal organic complex in solid loading, and also avoids the problems of environmental pollution and high toxicity caused by introducing chloromethyl through a highly toxic reagent such as chloromethyl methyl ether.

Description

Technical Field

[0001] This invention relates to the field of heterogeneous metal-organic photocatalyst preparation technology, specifically to a metal-organic complex supported catalyst, its preparation method, and its application. Background Technology

[0002] Organometallic complexes (MMCs) have wide applications in medicinal chemistry, photochemistry, electrochemistry, biochemistry, and materials chemistry due to their diverse ligands and unique luminescent properties. In photocatalysis, MMCs primarily function as photocatalysts, making significant contributions to environmental remediation, photocatalytic water splitting, carbon dioxide emission reduction, and organic synthesis. Due to their high visible light absorption, limited light scattering, high quantum yield, and light transport characteristics, MMCs exhibit excellent catalytic performance in homogeneous photocatalytic systems. However, factors such as high cost, toxicity, and natural scarcity make the heterogeneous development of homogeneous catalysts inevitable. Heterogeneous metal catalysis, with its recyclability and reusability of MMCs, significantly reduces catalytic reaction costs and has gained popularity, finding applications in practical industrial production.

[0003] Currently, the loading process for organometallic complexes is quite cumbersome, often involving a series of substitution reactions followed by copolymerization, or a multi-step post-modification strategy, which significantly increases preparation time and cost. Furthermore, heterogeneous photocatalysis also faces challenges related to electron-hole recombination or energy loss, necessitating a support platform to shorten energy transport distances or reduce electron-hole recombination. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a metal-organic complex supported catalyst, its preparation method, and its application, thereby solving the problems of cumbersome and polluting processes associated with existing metal-organic complexes in immobilized environments.

[0005] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for preparing a metal-organic complex supported catalyst is provided, comprising the following steps:

[0006] Hollow mesoporous polystyrene nanospheres, fac-Ir(ppy)3 and DCE were mixed and swollen for 1.5-2.5 h. FeCl3 was added and reacted at 50-70 °C for 10-15 h. After washing and drying, HMPNs(S)@Ir, i.e., metal-organic complex supported catalyst, was obtained.

[0007] Based on the above technical solution, the present invention can be further improved as follows:

[0008] Furthermore, it is mixed in an Ar atmosphere.

[0009] Furthermore, the mass-to-volume ratio of hollow mesoporous polystyrene nanospheres, fac-Ir(ppy)3, FeCl3, and DCE is 80-120 mg: 60-70 mg: 80-85 mg: 25-35 mL.

[0010] Furthermore, the mass-to-volume ratio of hollow mesoporous polystyrene nanospheres, fac-Ir(ppy)3, FeCl3, and DCE was 100 mg: 65 mg: 83 mg: 30 mL.

[0011] Furthermore, ethanol was used for washing.

[0012] Furthermore, the hollow mesoporous polystyrene nanospheres are low-crosslinked hollow mesoporous polystyrene nanospheres, medium-crosslinked hollow mesoporous polystyrene nanospheres, or hyper-crosslinked hollow mesoporous polystyrene nanospheres.

[0013] Furthermore, low-crosslinked hollow mesoporous polystyrene nanospheres were prepared by the following method:

[0014] (1) Disperse polystyrene microspheres uniformly in PVA solution and stir at room temperature to obtain polystyrene microsphere dispersion emulsion; mix styrene, VBC, PVA solution and F127, stir, then add polystyrene microsphere dispersion emulsion dropwise, stir twice, add KPS solution, heat to 60-70℃ and react for 70-100 min to obtain reaction solution;

[0015] (2) Add styrene, VBC and DVB dropwise to the reaction solution obtained in step (1), heat to 80-90℃ and react for 20-25h, and finally cool, centrifuge and wash to obtain CS-I;

[0016] (3) Stir the CS-I obtained in step (2) in a mixture of tetrahydrofuran and ethanol for 10-15 h, centrifuge, then stir in a mixture of ethanol and acetone for 10-15 h, centrifuge again, and air dry to obtain low cross-linked hollow mesoporous polystyrene nanospheres.

[0017] Furthermore, in steps (1) and (2), the molar ratio of styrene, VBC and DVB is 2.6-3.4:1.6-2.4:0.8-1.2.

[0018] Furthermore, in steps (1) and (2), the molar ratio of styrene, VBC, and DVB is 3:2:1.

[0019] Furthermore, in step (1), the mass-to-volume ratio of polystyrene microspheres to PVA solution is 380-420 mg: 18-22 mL.

[0020] Furthermore, in step (1), the mass-to-volume ratio of polystyrene microspheres to PVA solution is 400 mg: 20 mL.

[0021] Furthermore, in step (1), the concentration of the PVA solution is 0.5 wt%.

[0022] Furthermore, in step (1), the mixture is stirred at room temperature for 20-25 hours.

[0023] Furthermore, in step (1), styrene, VBC, PVA solution and F127 are mixed under an Ar atmosphere.

[0024] Furthermore, in step (1), the molar volume ratio of styrene, VBC, F127 and PVA solution is 1.8-2.2 mmol: 0.8-1.2 mmol: 0.03-0.05 mmol: 15-22 mL.

[0025] Furthermore, in step (1), the molar volume ratio of styrene, VBC, F127 and PVA solution is 2 mmol: 1 mmol: 0.04 mmol: 20 mL.

[0026] Furthermore, in step (1), the molar ratio of polystyrene microspheres to styrene is 380-420 mg: 1.8-2.2 mol.

[0027] Furthermore, in step (1), stir at 20-30℃ for 4-6 minutes.

[0028] Furthermore, in step (1), stir at 25°C for 5 minutes.

[0029] Furthermore, in step (1), the mixture is stirred twice at 20-30℃ for 3-5 hours.

[0030] Furthermore, in step (1), the mass-to-volume ratio of polystyrene microspheres to KPS solution is 380-420 mg: 7-9 mL.

[0031] Furthermore, in step (1), the concentration of the KPS solution is 30-33 mmol / L.

[0032] Furthermore, in step (2), the molar ratio of styrene, VBC and DVB is 0.8-1.2:0.8-1.2:0.8-1.2.

[0033] Furthermore, in step (2), the molar ratio of styrene, VBC and DVB is 1:1:1.

[0034] Furthermore, in step (2), the molar ratio of styrene to styrene in step (1) is 0.8-1.2:1.8-2.2.

[0035] Furthermore, in step (2), centrifuge at 10000-15000 rpm for 4-6 min.

[0036] Furthermore, in step (2), the centrifuge at 13000 rpm for 5 min.

[0037] Furthermore, in step (2), distilled water and ethanol are used for washing.

[0038] Furthermore, in step (3), the mixture of tetrahydrofuran and ethanol is stirred at 20-30°C.

[0039] Furthermore, in step (3), the mixture of ethanol and acetone is stirred at 60-70°C.

[0040] Furthermore, in step (3), the volume ratio of tetrahydrofuran to ethanol is 1:1.

[0041] Furthermore, in step (3), the volume ratio of ethanol to acetone is 1:1.

[0042] Furthermore, in step (3), the volume-to-mass ratio of the mixture of tetrahydrofuran and ethanol to the polystyrene microspheres in step (1) is 25-35 mL: 380-420 mg.

[0043] Furthermore, when the molar ratio of styrene, VBC and DVB in steps (1) and (2) is 1.8-2.2:1.8-2.2:2.8-3.2, the hollow mesoporous polystyrene nanospheres obtained in step (3) are moderately cross-linked hollow mesoporous polystyrene nanospheres.

[0044] Furthermore, when the molar ratio of styrene, VBC and DVB in steps (1) and (2) is 2:2:3, the hollow mesoporous polystyrene nanospheres obtained in step (3) are moderately cross-linked hollow mesoporous polystyrene nanospheres.

[0045] Furthermore, hypercrosslinked hollow mesoporous polystyrene nanospheres were prepared by the following method:

[0046] S1: Hollow mesoporous polystyrene nanospheres with low cross-linking degree, HAc, FDA and FeCl3 were mixed and reacted at 75-85℃ for 3-5h. After centrifugation, washing and vacuum drying, a white solid was obtained.

[0047] S2: The white solid obtained in step S1 is swollen with a mixed solution of DCE and FDA for 1.5-2.5 h, then FeCl3 is added, and the mixture is reacted at 75-85℃ for 10-15 h. After washing and drying, highly cross-linked hollow mesoporous polystyrene nanospheres are obtained.

[0048] Furthermore, in step S1, the mass-to-volume ratio of the low-crosslinked hollow mesoporous polystyrene nanospheres, FeCl3, HAc, and FDA is 480-520 mg: 8-12 g: 35-45 mL: 5-6 mL.

[0049] Furthermore, in step S1, the mass-to-volume ratio of the low-crosslinked hollow mesoporous polystyrene nanospheres, FeCl3, HAc, and FDA is 500 mg: 10 g: 40 mL: 5.6 mL.

[0050] Furthermore, in step S1, the product is washed sequentially with acetone, 1 mol / L hydrochloric acid, and water.

[0051] Furthermore, in step S1, vacuum drying is performed at 35-45℃.

[0052] Furthermore, in step S2, the volume-to-mass ratio of DCE, FDA, and FeCl3 is 35-45 mL: 5-6 mL: 8-12 g.

[0053] Furthermore, in step S2, the mass ratio of FeCl3 to FeCl3 in step (1) is 1:0.8-1.2.

[0054] Furthermore, in step S2, the mass ratio of FeCl3 to FeCl3 in step (1) is 1:1.

[0055] Furthermore, in step S2, the sample is washed three times each with acetone, 1 mol / L hydrochloric acid, and water.

[0056] Furthermore, in step S2, drying is carried out at 55-65°C.

[0057] Further, in step (1), polystyrene microspheres are prepared by the following method: styrene, distilled water and PVP are mixed and stirred, then KPS and deionized water are added, stirred twice, and then heated to 80-90℃ for 20-25h. Finally, after centrifugation, washing and drying, polystyrene microspheres are obtained.

[0058] Furthermore, styrene, distilled water, and PVP were mixed in an Ar atmosphere.

[0059] Furthermore, the mass-to-volume ratio of styrene, PVP, KPS, distilled water, and deionized water is 8-8.5g: 1-2g: 0.4-0.5g: 150-200mL: 8-10mL.

[0060] Furthermore, the mass-to-volume ratio of styrene, PVP, KPS, distilled water, and deionized water is 8.2 g: 1.65 g: 0.45 g: 180 mL: 9 mL.

[0061] Further, stir at room temperature for 10-20 minutes.

[0062] Further, stir at room temperature for 10-20 minutes.

[0063] Furthermore, it is washed with deionized water and ethanol in sequence.

[0064] The present invention also provides a metal-organic complex supported catalyst prepared by the above method.

[0065] The present invention also provides the application of the above-mentioned organometallic complex supported catalyst in heterogeneous photocatalysis.

[0066] The present invention has the following beneficial effects:

[0067] 1. This application uses hollow mesoporous polystyrene nanospheres (HMPNs) prepared by copolymerization of styrene and p-vinylbenzyl chloride as a carrier platform to prepare HMPNs with low (S L )), and (HMPNs(S) M )), Super (HMPNs (S) H Crosslinked HMPNs can be directly anchored to the HMPN framework in a one-pot manner via FeCl3-catalyzed FC alkylation reaction, providing a simple and convenient anchoring strategy for organometallic complexes. At the same time, the porous, thin-shell, and hollow structure and morphology of the HMPNs loaded with the organometallic complex fac-Ir(ppy)3 enable the substrate to quickly reach the active site of the catalyst through the pores, effectively avoiding energy loss or electron-hole recombination during the energy transfer process, thereby improving the catalytic efficiency and reducing the reaction cost.

[0068] 2. This invention utilizes a one-pot method to link fac-Ir(ppy)3, containing a benzene ring, to the carbon atom of the benzyl chloride group in the support HMPNs via Friedel-Crafts alkylation, thereby anchoring this organometallic complex photocatalyst in a low-cost manner. This solves the problem of cumbersome modification processes for organometallic complexes in immobilization and avoids the environmental pollution and high toxicity issues associated with traditional methods of introducing chloromethyl groups using reagents such as chloromethyl ether. Attached Figure Description

[0069] Figure 1 Preparation routes for hollow mesoporous polystyrene with different degrees of crosslinking;

[0070] Figure 2 This describes a route for preparing organometallic complex-supported catalysts.

[0071] Figure 3 Here is a SEM image of the polystyrene microspheres prepared in Example 1;

[0072] Figure 4 The particle size distribution diagram is shown for the polystyrene microspheres prepared in Example 1.

[0073] Figure 5 The images show the SEM images and particle size distribution of CS-I obtained in Example 1.

[0074] Figure 6 HMPNs (S) prepared in Example 1 L SEM images and particle size distribution maps of the particles;

[0075] Figure 7 HMPNs (S) prepared in Example 4 M SEM images and particle size distribution maps of the particles;

[0076] Figure 8 HMPNs (S) prepared in Example 5 H SEM images and particle size distribution maps of the particles;

[0077] Figure 9 HMPNs (S) prepared in Example 1 L TEM image;

[0078] Figure 10 HMPNs (S) prepared in Example 5 H TEM image;

[0079] Figure 11 HMPNs (S) prepared in Example 1 L TEM-Mapping plot of @Ir;

[0080] Figure 12 For example, fac-Ir(ppy)3 and HMPNs(S) in Example 1 L ) and HMPNs(S L Infrared absorption spectrum of )@Ir;

[0081] Figure 13 For HMPNs(S) in Example 1 L ) and HMPNs(S L )@Ir solid state 13 C NMR spectrum;

[0082] Figure 14 The UV-Vis absorption spectra of fac-Ir(ppy)3 in different solvents;

[0083] Figure 15 HMPNs (S) prepared in Example 1 L UV-Vis absorption spectra of Ir in different solvents;

[0084] Figure 16 HMPNs (S) prepared in Example 1 L Isothermal adsorption-desorption curves of )@Ir;

[0085] Figure 17 HMPNs (S) prepared in Example 1 L Aperture distribution map of @Ir;

[0086] Figure 18 The product of the HMPNs(S)@Ir catalytic reaction prepared in Example 1 1 H-NMR spectrum. Detailed Implementation

[0087] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0088] Example 1:

[0089] A metal-organic complex supported catalyst is prepared by the following steps:

[0090] (1) Preparation of polystyrene microspheres

[0091] Under an Ar atmosphere, 8.2 g of styrene, 180 mL of distilled water, and 1.65 g of PVP were mixed in a 500 mL three-necked flask and stirred at room temperature for 15 min. Then, 0.45 g of KPS and 9 mL of deionized water were added, and the mixture was stirred at room temperature for another 15 min. The mixture was then heated to 85 °C and reacted for 24 h. Finally, the mixture was centrifuged at 13000 rpm for 5 min and washed successively with deionized water and ethanol until the supernatant was colorless, clear, and transparent. After drying, 6.5 g of white solid powder was obtained, thus preparing polystyrene microspheres.

[0092] (2) Preparation of low-crosslinked hollow mesoporous polystyrene nanospheres (preparation route see...) Figure 1 )

[0093] (2.1) 400 mg of polystyrene microspheres obtained in step (1) were uniformly dispersed in 20 mL of PVA solution (0.5 wt%) and stirred at room temperature for 24 h to obtain a polystyrene microsphere dispersion emulsion; under Ar atmosphere, 2 mmol of styrene, 1 mmol of VBC, 20 mL of PVA solution (0.5 wt%) and 0.04 mmol of F127 were mixed in a 150 mL three-necked flask and stirred at 25 °C for 5 min. Then, the polystyrene microsphere dispersion emulsion was added dropwise and stirred again at 25 °C for 4 h. 8 mL of KPS solution (32.5 mmol / L) was added and the temperature was raised to 65 °C and reacted for 80 min to obtain the reaction solution.

[0094] (2.2) Add 1 mmol of styrene, 1 mmol of VBC and 1 mmol of DVB to the reaction solution obtained in step (2.1), heat to 85℃ and react for 24 h, finally cool, centrifuge at 13000 rpm for 5 min, wash with distilled water and ethanol until the supernatant is colorless, clear and transparent, and obtain white solid CS-I.

[0095] (2.3) Dissolve the CS-I obtained in step (2.2) in a mixture of tetrahydrofuran and ethanol (V THF / V ethanol =15mL / 15mL) stirred for 12 hours, centrifuged at 10000 rpm for 5 minutes, and then in a mixture of ethanol and acetone (V ethanol / V actone =15mL / 15mL) Stir for 12 hours, centrifuge twice at 13000rpm for 5 minutes, and air dry to obtain a white solid, namely low cross-linked hollow mesoporous polystyrene nanospheres (HMPNs(S)). L ));

[0096] (3) Preparation of metal-organic complex supported catalysts (see preparation route) Figure 2 )

[0097] In an Ar atmosphere, 100 mg of the low-crosslinked hollow mesoporous polystyrene nanospheres prepared in step (2.3), 65 mg of fac-Ir(ppy)3, and 30 mL of DCE were mixed in a 100 mL round-bottom flask and allowed to swell for 2 h. Then, 83 mg of FeCl3 was added, and the mixture was reacted at 60 °C for 12 h. The mixture was washed with ethanol and dried to obtain a yellow solid HMPNs(S L )@Ir, i.e., metal-organic complex supported catalyst.

[0098] Example 2:

[0099] A metal-organic complex supported catalyst is prepared by the following steps:

[0100] (1) Preparation of polystyrene microspheres

[0101] Under an Ar atmosphere, 8 g of styrene, 150 mL of distilled water, and 1 g of PVP were mixed in a 500 mL three-necked flask and stirred at room temperature for 10 min. Then, 0.4 g of KPS and 8 mL of deionized water were added, and the mixture was stirred at room temperature for another 10 min. The mixture was then heated to 80 °C and reacted for 25 h. Finally, the mixture was centrifuged at 13000 rpm for 5 min and washed successively with deionized water and ethanol until the supernatant was colorless, clear, and transparent. After drying, a white solid powder was obtained, and polystyrene microspheres were prepared.

[0102] (2) Preparation of low-crosslinked hollow mesoporous polystyrene nanospheres

[0103] (2.1) 380 mg of polystyrene microspheres obtained in step (1) were uniformly dispersed in 18 mL of PVA solution (0.5 wt%) and stirred at room temperature for 20 h to obtain a polystyrene microsphere dispersion emulsion; under Ar atmosphere, 1.8 mmol of styrene, 0.8 mmol of VBC, 15 mL of PVA solution (0.5 wt%) and 0.03 mmol of F127 were mixed in a 150 mL three-necked flask and stirred at 20 °C for 6 min. Then, the polystyrene microsphere dispersion emulsion was added dropwise and stirred again at 20 °C for 5 h. 7 mL of KPS solution (30 mmol / L) was added and the temperature was raised to 60 °C and reacted for 100 min to obtain the reaction solution.

[0104] (2.2) Add 0.8 mmol styrene, 0.8 mmol VBC and 0.8 mmol DVB dropwise to the reaction solution prepared in step (2.1), heat to 80℃ and react for 25 h, finally cool, centrifuge at 13000 rpm for 5 min, wash with distilled water and ethanol until the supernatant is colorless, clear and transparent, to obtain white solid CS-I.

[0105] (2.3) Dissolve the CS-I obtained in step (2.2) in a mixture of tetrahydrofuran and ethanol (V THF / V ethanol =15mL / 15mL) Stir for 10 hours, centrifuge at 10000 rpm for 5 minutes, and then place in a mixture of ethanol and acetone (V ethanol / V actone =15mL / 15mL) Stir for 10 hours, centrifuge twice at 13000rpm for 5 minutes, and air dry to obtain a white solid, namely low cross-linked hollow mesoporous polystyrene nanospheres (HMPNs(S)). L ));

[0106] (3) Preparation of metal-organic complex supported catalysts

[0107] In an Ar atmosphere, 80 mg of the low-crosslinked hollow mesoporous polystyrene nanospheres prepared in step (2.3), 60 mg of fac-Ir(ppy)3, and 25 mL of DCE were mixed in a 100 mL round-bottom flask and allowed to swell for 1.5 h. Then, 80 mg of FeCl3 was added, and the mixture was reacted at 50 °C for 15 h. The mixture was washed with ethanol and dried to obtain a yellow solid HMPNs(S L )@Ir, i.e., metal-organic complex supported catalyst.

[0108] Example 3:

[0109] A metal-organic complex supported catalyst is prepared by the following steps:

[0110] (1) Preparation of polystyrene microspheres

[0111] Under an Ar atmosphere, 8.5 g of styrene, 200 mL of distilled water, and 2 g of PVP were mixed in a 500 mL three-necked flask and stirred at room temperature for 20 min. Then, 0.5 g of KPS and 10 mL of deionized water were added, and the mixture was stirred at room temperature for another 20 min. The mixture was then heated to 90 °C and reacted for 20 h. Finally, the mixture was centrifuged at 13000 rpm for 5 min and washed successively with deionized water and ethanol until the supernatant was colorless, clear, and transparent. After drying, g of white solid powder was obtained, thus preparing polystyrene microspheres.

[0112] (2) Preparation of low-crosslinked hollow mesoporous polystyrene nanospheres

[0113] (2.1) 420 mg of polystyrene microspheres obtained in step (1) were uniformly dispersed in 22 mL of PVA solution (0.5 wt%) and stirred at room temperature for 25 h to obtain a polystyrene microsphere dispersion emulsion; under Ar atmosphere, 2.2 mmol of styrene, 1.2 mmol of VBC, 22 mL of PVA solution (0.5 wt%) and 0.05 mmol of F127 were mixed in a 150 mL three-necked flask and stirred at 30 °C for 4 min. Then, the polystyrene microsphere dispersion emulsion was added dropwise and stirred again at 30 °C for 3 h. 9 mL of KPS solution (33 mmol / L) was added and the temperature was raised to 70 °C for 70 min to obtain the reaction solution.

[0114] (2.2) Add 1.2 mmol of styrene, 1.2 mmol of VBC and 1.2 mmol of DVB to the reaction solution prepared in step (2.1), heat to 90℃ and react for 20 h, then cool, centrifuge at 13000 rpm for 5 min, wash with distilled water and ethanol until the supernatant is colorless, clear and transparent, to obtain white solid CS-I.

[0115] (2.3) Dissolve the CS-I obtained in step (2.2) in a mixture of tetrahydrofuran and ethanol (VTHF / V ethanol =15mL / 15mL) stirred for 15 hours, centrifuged at 10000 rpm for 5 minutes, and then in a mixture of ethanol and acetone (V ethanol / V actone =15mL / 15mL) Stir for 15 hours, centrifuge twice at 13000 rpm for 5 minutes, and air dry to obtain a white solid, namely low crosslinked hollow mesoporous polystyrene nanospheres (HMPNs(S)). L ));

[0116] (3) Preparation of catalysts supported on organic complexes

[0117] In an Ar atmosphere, 120 mg of the low-crosslinked hollow mesoporous polystyrene nanospheres prepared in step (2.3), 70 mg of fac-Ir(ppy)3, and 35 mL of DCE were mixed in a 100 mL round-bottom flask and allowed to swell for 2.5 h. Then, 85 mg of FeCl3 was added, and the mixture was reacted at 70 °C for 10 h. The mixture was washed with ethanol and dried to obtain a yellow solid HMPNs(S L )@Ir, i.e., metal-organic complex supported catalyst.

[0118] Example 4:

[0119] A metal-organic complex supported catalyst is prepared by the following steps:

[0120] In step (2.1), the amount of styrene is 1 mmol;

[0121] In step (2.2), the DVB concentration is 3 mmol.

[0122] In step (2.3), the white solid obtained is a medium-crosslinked hollow mesoporous polystyrene nanosphere (HMPNs(S)). M (See preparation route) Figure 1 )

[0123] In step (3), yellow solid HMPNs(S) were prepared. M @Ir, i.e., organometallic complex supported catalyst. (See preparation route for details.) Figure 2 )

[0124] The rest is the same as in Example 1.

[0125] Example 5:

[0126] A metal-organic complex supported catalyst is prepared by the following steps:

[0127] 500 mg of the low-crosslinked hollow mesoporous polystyrene nanospheres prepared in step (2.3) were mixed with 40 mL of HAc, 5.6 mL of FDA, and 10 g of FeCl3. The mixture was reacted at 80 °C for 4 h, centrifuged at 10,000 rpm for 5 min, and washed three times each with acetone, 1 mol / L hydrochloric acid, and water, respectively. The mixture was then dried under vacuum at 40 °C to obtain a white solid. The solid was swollen with a mixed solution of 40 mL of DCE and 5.6 mL of FDA for 2 h, and then 10 g of FeCl3 was added. The mixture was reacted at 80 °C for 12 h, washed three times each with acetone, 1 mol / L hydrochloric acid, and water, respectively, and dried at 60 °C to obtain highly crosslinked hollow mesoporous polystyrene nanospheres. (See preparation route for details.) Figure 1 )

[0128] In step (3), yellow solid HMPNs(S) were prepared. H @Ir, i.e., organometallic complex supported catalyst. (See preparation route for details.) Figure 2 )

[0129] The rest is the same as in Example 1.

[0130] Test case

[0131] I. The polystyrene microspheres prepared in Example 1 were subjected to SEM analysis and particle size distribution analysis. The results are shown in the figure. Figure 3-4 .

[0132] Depend on Figure 3-4 It can be seen that the polystyrene microspheres have regular morphology and uniform particle size, with a particle size of 140 nm.

[0133] II. The CS-I and HMPNs(S) prepared in Example 1 L HMPNs (S) prepared in Example 4 M ) and HMPNs (S) prepared in Example 5 H SEM analysis was performed on the HMPNs (S) prepared in Example 1, and the HMPNs (S) were analyzed. L ) and HMPNs (S) prepared in Example 5 H TEM detection was performed, and the results are shown below. Figure 5-10 .

[0134] Depend on Figure 5 It can be seen that the white solid CS-I has a particle size of 180 nm and a regular morphology;

[0135] Depend on Figure 6 It can be seen that the white solid HMPNs (S L The particles have a diameter of 182 nm and a regular morphology.

[0136] Depend on Figure 7 It can be seen that the white solid HMPNs (S MThe particles have a diameter of 193 nm and a regular morphology.

[0137] Depend on Figure 8 It can be seen that the white solid HMPNs (S H The particles have a diameter of 206 nm and a regular morphology.

[0138] Depend on Figure 9-10 It can be seen that HMPNs(S) L ) and HMPNs(S H The fact that it has a hollow structure indicates that the present invention has successfully prepared hollow HMPNs.

[0139] III. The HMPNs(S) prepared in Example 1 L TEM-Mapping characterization was performed using )@Ir, and the results are shown in [the table]. Figure 11 .

[0140] Depend on Figure 11 It can be seen that HMPNs(S) L The fac-Ir(ppy)3 particles retain their hollow structure and exhibit uniform particle size and regular morphology. TEM-mapping characterization reveals the presence of C, Ir, and N elements, indicating successful anchoring of fac-Ir(ppy)3 on HMPNs. TEM-mapping C and N characterizations show that fac-Ir(ppy)3 is distributed in a hollow ring shape on the support, indicating that the photocatalyst is uniformly distributed on the inner and outer surfaces of the support.

[0141] IV. Identification

[0142] 1. Combine fac-Ir(ppy)3 with HMPNs(S) prepared in Example 1. L ) and HMPNs(S L Infrared absorption spectroscopy was performed using )@Ir, and the results are shown below. Figure 12 .

[0143] Depend on Figure 12 Therefore, in order to prove that fac-Ir(ppy)3 is successfully covalently anchored to HMPNs(S), this application selects HMPNs(S) L ), HMPNs(S L Infrared characterization was performed on )@Ir and fac-Ir(ppy)3.

[0144] HMPNs(S L The spectrum of ) is as follows Figure 12 As shown in (a): 3078, 3051, 3017, 2915, 2841 cm -1 This is the stretching vibration of the CH bond on the benzene ring; 1605 cm⁻¹ -1These are skeletal vibrations of the benzene ring; the in-plane and out-of-plane bending vibration peaks of the CH bonds on the benzene ring are at 1489 and 1418 cm⁻¹, respectively. -1 749, 695cm -1 This is an out-of-plane bending vibration of the CH bond following monosubstituted benzene ring; 1456, 675 cm⁻¹ -1 The characteristic absorption peak of -CH2Cl appeared; the former is the stretching vibration of the C-Cl bond in -CH2Cl, and the latter is the in-plane bending vibration of the CH bond in -CH2Cl; 824 cm⁻¹ -1 The absorption at [location] is due to the out-of-plane bending vibration of the CH bond on the benzene ring after disubstituted. Infrared spectroscopy indicates that the copolymerization of p-vinylbenzyl chloride with styrene was successful.

[0145] HMPNs(S L The spectrum of @Ir is as follows Figure 12 As shown in (b), the stretching vibration peak of C=N is between 1680 and 1500 cm⁻¹. -1 The stretching vibration peaks of phenylpyridine are at 1623, 1610 and 1591 cm⁻¹, respectively. -1 At these locations, after coordination with the iridium center, the blue shifts to 1605 and 1583 cm, respectively. -1 HMPNs(S) L 1605 and 1583 cm⁻¹ were also observed in the infrared absorption of )@Ir. -1 The characteristic absorption peak of fac-Ir(ppy)3. In addition, HMPNs(S L The text contains stretching vibration peaks (3078, 3051, 3017, 2915, 2841 cm⁻¹) on the CH bond of the benzene ring in polystyrene. -1 The in-plane and out-of-plane bending vibration peaks of the CH bonds on the benzene ring are at 1471 and 1418 cm⁻¹, respectively. -1 749, 695cm -1 Following monosubstituted benzene rings, the CH bond out-of-plane bending vibrations preserve the polystyrene structure well. After FC alkylation, the 1456 and 675 cm⁻¹ values ​​are observed. -1 The stretching vibration peak intensity of the C-Cl bond in -CH2Cl was significantly weakened. External spectroscopy indicated that fac-Ir(ppy)3 was successfully anchored to HMPNs(S).

[0146] 2. The HMPNs(S) prepared in Example 1 L ) and HMPNs(S L Solid-state carbon NMR spectroscopy was performed using )@Ir, and the results are shown in […]. Figure 13 .

[0147] Depend on Figure 13 It can be seen that, Figure 13 (a) is HMPNs 13The C-NMR spectrum shows that 146.33 ppm is the peak of the substituted benzene ring of polystyrene in HMPNs, 127.13 ppm is the peak of the unsubstituted polystyrene ring, 45.69 ppm is the -CH peak of polystyrene and p-vinylbenzyl chloride, 40.26 ppm is the -CH2 peak, and 65.25 ppm shows the -CH2Cl peak, indicating that the copolymerization of styrene and p-vinylbenzyl chloride was successful.

[0148] Figure 13 (b) shows HMPNs (S) prepared after FC alkylation. L After HMPNs were subjected to FC alkylation and fac-Ir(ppy)3 loading, HMPNs(S L @Ir exhibits the characteristic absorption peaks of HMPNs. The -CH2Cl peak at 65.25 ppm is still present, but its peak area has decreased. This is because the content of vinylbenzyl chloride during HMPN preparation is much higher than the content of fac-Ir(ppy)3 added during the loading process, resulting in incomplete reaction of -CH2Cl. Due to the coordination of iridium, the peak in the C=N region of the ligand phenylpyridine appears at ~165.67 ppm, and carbon signals on the benzene and pyridine rings are found at 136.07 and 119.79 ppm. This indicates that fac-Ir(ppy)3 is successfully covalently anchored to HMPNs.

[0149] 3. The fac-Ir(ppy)3 and the HMPNs(S) prepared in Example 1 were respectively... L @Ir was detected by UV-Vis absorption spectroscopy in different solvents, and the results are shown in [the table below]. Figure 14-15 .

[0150] Depend on Figure 14-15 It can be seen that the absorption of fac-Ir(ppy)3 is roughly the same, and in the wavelength ranges of ~246, ~256, and ~284 nm, it is mainly attributed to the phenylpyridine ligand centered on the ligand. 1 The absorption peak around 381 nm is mainly attributed to metal-ligand charge transfer (MLCT). Given the similar elemental compositions of the three supported catalysts, we selected HMPNs (S... L The absorption behavior of the supported catalyst in different solvents was studied.

[0151] HMPNs(S L The specific results of UV-Vis absorption in these solvents are as follows: Figure 15 As shown: HMPNs(S LLike fac-Ir(ppy)3, HMPNs@Ir also exhibits UV absorption around ~243, ~281, and ~381 nm, indicating that HMPNs@Ir was successfully prepared and that the supported catalyst retains the UV absorption characteristics of fac-Ir(ppy)3.

[0152] 4. The HMPNs(S) prepared in Example 1 L HMPNs (S) prepared in Example 4 M ) and HMPNs (S) prepared in Example 5 H The solid pore structure and isothermal adsorption-desorption curves were analyzed, and the results are shown in [Figure number missing]. Figure 16-17 .

[0153] Depend on Figure 16-17 It can be seen that HMPNs(S) L )@Ir、HMPNs(S M )@Ir and HMPNs(S H The specific surface areas of )@Ir are 23.9, 21.9, and 78.1 m², respectively. 2 g -1 Hypercrosslinked HMPNs (S H The specific surface area of ​​Ir is 78.1 m². 2 g -1 The largest pore size is found in narrow mesopores, primarily at 3.6 nm, while the smallest pore size and volume are observed. This is because during the loading process, the support undergoes FC alkylation with fac-Ir(ppy)3 and simultaneously undergoes hypercrosslinking polymerization with its own chloromethyl groups. At 80 °C, more sites on the crosslinks tend to bridge via methylene groups, leading to an increase in specific surface area and a predominance of narrow mesopore sizes. N2 adsorption-desorption experiments demonstrate that HMPNs(S)@Ir possesses a mesoporous structure.

[0154] V. HMPNs(S) L Ir-catalyzed chalcone [2+2] cycloaddition reaction

[0155] Under an Ar atmosphere, Trans-chalcone (0.2 mmol, 42 mg) and 3 mmol% HMPNs (S) were added to a 10 mL reaction tube. L The product was reacted with 2 mL of Ir and 2 mL of CH3OH under 4 W blue light and 25 °C for 24 h, and separated by column chromatography (petroleum ether / ethyl acetate = 20 / 1) to give 28 mg of the product. 1 H-NMR see Figure 18 The following is a spectral analysis:

[0156] DL-((1R,2R,3S,4S)-3,4-diphenylcyclobutane-1,2-diyl)bis(phenylmethanone)(1):White solid. 1 H NMR (600MHz, DMSO): δ7.78(d,J=7.7Hz,4H),7.54(t,J=7.3Hz,2H),7.36(t,J=7.6Hz,4H ),7.34–7.28(m,8H),7.27–7.22(m,2H),4.60(dd,J=8.9Hz,2H),3.88(d,J=8.9Hz,2H).

[0157] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a metal-organic complex supported catalyst, characterized in that, Includes the following steps: Hollow mesoporous polystyrene nanospheres, fac-Ir(ppy)3 and DCE were mixed and swollen for 1.5-2.5 h. FeCl3 was added and reacted at 50-70 °C for 10-15 h. After washing and drying, HMPNs(S)@Ir, i.e., metal-organic complex supported catalyst, was obtained. The hollow mesoporous polystyrene nanospheres are low-crosslinked hollow mesoporous polystyrene nanospheres, medium-crosslinked hollow mesoporous polystyrene nanospheres, or hypercrosslinked hollow mesoporous polystyrene nanospheres. The low-crosslinking degree hollow mesoporous polystyrene nanospheres were prepared by the following method: (1) Disperse polystyrene microspheres uniformly in PVA solution and stir at room temperature to obtain polystyrene microsphere dispersion emulsion; mix styrene, VBC, PVA solution and F127, stir, then add polystyrene microsphere dispersion emulsion dropwise, stir twice, add KPS solution, heat to 60-70℃ and react for 70-100 min to obtain reaction solution; (2) Add styrene, VBC and DVB dropwise to the reaction solution obtained in step (1), heat to 80-90℃ and react for 20-25h. Finally, after cooling, centrifugation and washing, CS-I is obtained. (3) Stir the CS-I obtained in step (2) in a mixture of tetrahydrofuran and ethanol for 10-15 h, centrifuge, then stir in a mixture of ethanol and acetone for 10-15 h, centrifuge again, and air dry to obtain low cross-linked hollow mesoporous polystyrene nanospheres. In steps (1) and (2), the molar ratio of styrene, VBC and DVB is 2.6-3.4:1.6-2.4:0.8-1.2; The medium-crosslinked hollow mesoporous polystyrene nanospheres were prepared by the following method: In steps (1) and (2) of the method for preparing low-crosslinked hollow mesoporous polystyrene nanospheres, when the molar ratio of styrene, VBC and DVB is 1.8-2.2:1.8-2.2:2.8-3.2, the hollow mesoporous polystyrene nanospheres obtained in step (3) are moderately crosslinked hollow mesoporous polystyrene nanospheres; The hypercrosslinked hollow mesoporous polystyrene nanospheres were prepared by the following method: S1: Hollow mesoporous polystyrene nanospheres with low cross-linking degree, HAc, FDA and FeCl3 were mixed and reacted at 75-85℃ for 3-5h. After centrifugation, washing and vacuum drying, a white solid was obtained. S2: The white solid obtained in step S1 is swollen with a mixed solution of DCE and FDA for 1.5-2.5 h, then FeCl3 is added, and the mixture is reacted at 75-85℃ for 10-15 h. After washing and drying, highly cross-linked hollow mesoporous polystyrene nanospheres are obtained.

2. The method for preparing the organometallic complex supported catalyst according to claim 1, characterized in that, The mass-to-volume ratio of hollow mesoporous polystyrene nanospheres, fac-Ir(ppy)3, FeCl3 and DCE is 80-120 mg: 60-70 mg: 80-85 mg: 25-35 mL.

3. The method for preparing the organometallic complex supported catalyst according to claim 1, characterized in that, In step (1), polystyrene microspheres are prepared by the following method: styrene, distilled water and PVP are mixed and stirred, then KPS and deionized water are added, stirred twice, and then heated to 80-90℃ for 20-25h. Finally, after centrifugation, washing and drying, polystyrene microspheres are obtained.

4. The organometallic complex supported catalyst prepared by the method of any one of claims 1-3.

5. The application of the organometallic complex supported catalyst according to claim 4 in heterogeneous photocatalysis.

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