MOF composite material, and preparation method therefor and use thereof

Abstract

Disclosed in the present application are an MOF composite material, and a preparation method therefor and the use thereof. The MOF composite material comprises Cd-MOF and CdS, wherein a Cd metal cluster in the Cd-MOF is connected to one end of cysteamine, and the other end of the cysteamine is connected to CdS. The MOF composite material of the present application has good stability and catalytic efficiency performance for catalyzing a cyclization reaction of CO2 and propargylamine. Since the Cd metal cluster in the Cd-MOF is connected to one end of the cysteamine, and the other end of the cysteamine is connected to CdS, the synergistic effect of CdS and Cd-MOF greatly improves the catalysis of the cyclization reaction of CO2 and propargylamine.

Description

A MOFs composite material and its preparation method and application Technical Field

[0001] The present application relates to the technical field of metal organic framework materials, and in particular to a MOFs composite material and a preparation method and application thereof. Background Art

[0002] In recent years, carbon neutrality has attracted widespread attention because carbon dioxide (CO2) as a greenhouse gas has caused environmental and climate problems. CO2 is also a very promising C1 source in synthetic chemistry. It is more environmentally friendly and safer than traditional C1 sources such as CO. Oxazolidinone has good bactericidal activity and low toxicity to the human body, and is often used as an antibiotic in clinical medicine. The cyclization reaction of propargylamine with CO2 has become an effective method for synthesizing 2-oxazolidinone. However, in the CO2 and propargylamine cyclization reaction system, due to the kinetic inertness and thermodynamic stability of CO2, CO2 activation usually requires high temperature and high pressure, which will greatly reduce the recovery performance of the catalyst. Therefore, there is an urgent need to develop mild and precious metal-free photocatalysts to achieve the green conversion of carbon dioxide and propargylamine under normal temperature and pressure and light conditions, which is a huge challenge.

[0003] Therefore, it is necessary to develop a catalyst with high stability, high catalytic efficiency and can be used for the photocatalytic cyclization reaction of propargylamine with CO2 at room temperature and pressure.

[0004] Summary of the Invention

[0005] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, in a first aspect, the present application proposes a MOFs composite material with high cyclic stability and high catalytic efficiency, capable of photocatalyzing the cyclization reaction of propargylamine with CO2 at room temperature and pressure.

[0006] The second aspect of the present application also provides a method for preparing a MOFs composite material.

[0007] The third aspect of the present application also provides an application of a MOFs composite material.

[0008] According to an embodiment of the first aspect of the present application, a MOFs composite material is provided, comprising Cd-MOF and CdS; the Cd metal cluster in the Cd-MOF is connected to one end of cysteamine, and the other end of the cysteamine is connected to CdS.

[0009] The MOFs composite material according to the embodiment of the present application has at least the following beneficial effects:

[0010] The MOFs composite material of this application exhibits excellent stability and catalytic efficiency in the cyclization reaction of CO2 with propargylamine. This is because the Cd metal cluster in the Cd-MOF is connected to one end of cysteamine, and the other end of cysteamine is connected to CdS. The synergistic effect of CdS and Cd-MOF greatly enhances the catalytic performance of the cyclization reaction of CO2 with propargylamine.

[0011] According to some embodiments of the present application, the Cd-MOF is prepared from a ligand and a cadmium salt by a solvothermal method;

[0012] Wherein, the structural formula of the ligand is as follows:

[0013] According to an embodiment of the second aspect of the present application, a method for preparing a MOFs composite material is provided, comprising the following steps:

[0014] S1: heating Cd-MOF, cysteamine and solvent to react to obtain an intermediate;

[0015] S2: Add cadmium salt and thioacetamide in step S1 and continue the reaction to obtain the product.

[0016] According to some embodiments of the present application, in step S1, the temperature of the heating reaction is 60°C to 100°C.

[0017] According to some embodiments of the present application, in step S1, the molar ratio of Cd-MOF to cysteamine is (3-6):1.

[0018] According to some embodiments of the present application, in step S2, the molar ratio of the cadmium salt to thioacetamide is (0.5-2):1.

[0019] According to some embodiments of the present application, the solvent is selected from at least one of ethanol, methanol, ethyl acetate, water, and DMF.

[0020] According to some embodiments of the present application, the Cd-MOF is prepared by the following method:

[0021] The ligand, cadmium salt and organic solvent are mixed to undergo a solvothermal reaction to obtain Cd-MOF.

[0022] According to some embodiments of the present application, the temperature of the solvothermal reaction is 90°C to 150°C.

[0023] According to some embodiments of the present application, the solvent thermal reaction time is 12 hours to 84 hours.

[0024] According to some embodiments of the present application, the organic solvent is selected from at least one of dimethylformamide, ethanol, acetonitrile, and ethyl acetate.

[0025] According to some embodiments of the present application, the cadmium salt includes at least one of cadmium nitrate and cadmium acetate.

[0026] The third aspect of the present application provides an application of a MOFs composite material in the photocatalytic cyclization reaction of propargylamine and CO2.

[0027] Other features and advantages of the present application will be set forth in the following description, and in part will be apparent from the description, or may be learned by practicing the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0029] FIG1 is a graph showing the cyclic stability of the MOFs composite material prepared in Example 1 of the present application in the photocatalytic cyclization reaction of propargylamine and carbon dioxide. DETAILED DESCRIPTION

[0030] The following are specific embodiments of the present application, and the technical solutions of the present application are further described in conjunction with the embodiments, but the present application is not limited to these embodiments.

[0031] Unless otherwise specified, the reagents, methods and equipment used in this application are conventional reagents, methods and equipment in this technical field.

[0032] Example 1

[0033] Example 1 provides a MOFs composite material, the preparation method of which is as follows:

[0034] Synthesis of ligand:

[0035] The general reaction formula and preparation steps are as follows:

[0036] Step 1: A mixture of 2.97 g of 3-(methoxycarbonyl)phenylboronic acid (16.5 mmol), 1.42 g of 1,3,6,8-tetrabromopyrene (2.75 mmol), 3.0 g of potassium carbonate (22 mmol), and 40 mL of dioxane was stirred at room temperature under nitrogen for 30 minutes, followed by the addition of 0.05 g of tetrakis(triphenylphosphine)palladium (0.045 mmol). The reaction mixture was refluxed for 3 days. After cooling to room temperature, the reaction mixture was poured into 150 mL of aqueous solution containing concentrated hydrochloric acid (3:1). The yellow suspension solution was extracted with chloroform (100 mL x 3), and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation under vacuum to obtain 1,3,6,8-tetrakis(3-methoxycarbonylphenyl)pyrene in a 76% yield.

[0037] Step 2: Dissolve 2.5 g of 1,3,6,8-tetrakis(3-methoxycarbonylphenyl)pyrene in 160 mL of THF. Add 10 g of NaOH aqueous solution (160 mL) while stirring. Stir and reflux for 72 hours. Remove the organic solvent in vacuo and filter the mixture. Adjust the pH of the filtrate to 1 with concentrated hydrochloric acid. The resulting yellow solid is collected by filtration, washed with water and methanol, and dried in a vacuum oven to obtain the ligand (H4PTTB) with a yield of 98%.

[0038] The hydrogen spectrum data are as follows:

[0039] 1 H NMR(500MHz,DMSO-d6)δ13.14(s,4H),8.24(s,4H),8.17(s,4H),8.11(t,J=6.2Hz,4H),8.08(s,2H),8.00 (d,J=7.8Hz,4H),7.75(t,J=7.7Hz,4H).FT-IR(KBr)ν3428(br),3176(br),1709(s),1244(m),1091(m)cm -1 .

[0040] Synthesis of Cd-MOFs

[0041] H4PTTB (69 mg, 0.1 mmol), Cd(NO3)2·4H2O (206 mg, 0.667 mmol), dimethylformamide (DMF, 3.5 mL), and H2O (1 mL) were placed in a sealed glass vial and heated to 100°C in an oven. After 72 h, orange-yellow blocky crystals (82.4 mg, 87.6% yield based on H4PTTB) were obtained and air-dried.

[0042] Synthesis of MOFs composites

[0043] S1: Suspend 120 mg of activated Cd-MOFs in 60 mL of anhydrous ethanol. Add 120 mg of cysteamine to the suspension, heat with stirring, and reflux at 80°C for 1 h.

[0044] S2: 132.6 mg of Cd(CH3COO)2·2H2O and 37.2 mg of thioacetamide were added and refluxed for 12 h. The resulting MOFs composite material (named: CdS@Cd-MOFs) was centrifuged and washed twice with deionized water and dried at 60°C.

[0045] Test Example 1

[0046] The MOFs composite material prepared in Example 1 was used to catalyze the cyclization reaction of propargylamine with CO2, as follows:

[0047] Preparation of propargylamine compounds

[0048] The general reaction formula and preparation steps are as follows:

[0049] Under stirring at room temperature, 3-bromopropyne (4 mmol) was added dropwise to a 25 mL glass bottle containing an amino compound (20 mmol) via a constant pressure dropping funnel over 30 minutes and magnetically stirred for 12 hours. After the reaction, the reaction solution was diluted with Et2O and washed with saturated aqueous NaHCO3 (3 × 25 mL). The extracted organic phase was concentrated by rotary evaporation and purified by silica gel column chromatography (PE:EA = 10:1) to obtain a yellow oily product.

[0050] Propargylamine compounds 1a-6a were prepared by the above preparation method.

[0051] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.5). 1 H NMR (500MHz, CDCl3) δ7.42–7.26(m,5H),3.88(s,2H),3.42(d,J=2.2Hz,2H),2.28(t,J=2.1Hz,1H),1.68(s,1H).

[0052] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4). 1 H NMR (500MHz, CDCl3) δ7.29 (dd, J=6.0, 2.4Hz, 2H), 6.89 (d, J=8.6Hz, 2H), 3.84 (d, J=2.2Hz, 2H ), 3.81 (d, J = 2.6Hz, 3H), 3.43 (t, J = 2.5Hz, 2H), 2.28 (d, J = 2.4Hz, 1H), 1.75 (d, J = 16.0Hz, 1H).

[0053] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.6). 1 H NMR (500MHz, CDCl3) δ7.33(dt,J=8.3,4.2Hz,2H),7.07–6.94(m,2H),3.87(s,2H),3.43(t,J=4.1Hz,2H),2.29(t,J=2.4Hz,1H),1.70(s,1H).

[0054] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.6). 1 H NMR(500MHz, CDCl3) δ3.40(d,J=2.4Hz,2H),2.50(d,J=6.7Hz,2H),2.19(s,1H),1.70 (d,J=15.5Hz,5H),1.44(dd,J=6.6,3.3Hz,2H),1.30–1.09(m,3H),1.01–0.85(m,2H).

[0055] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4). 1 H NMR (500MHz, CDCl3) δ7.40–7.24(m,5H),4.02(q,J=6.6Hz,1H),3.36(dd,J=17.1,2. 5Hz, 1H), 3.16 (dd, J = 17.1, 2.4Hz, 1H), 2.22 (t, J = 2.4Hz, 1H), 1.37 (d, J = 6.6Hz, 3H).

[0056] Cyclization reaction of propargylamine with CO2:

[0057] The propargylamine compounds 1a-6a prepared above, 1,1,3,3-tetramethylguanidine (TMG, 11.5 mg, 0.1 mmol), CdS@Cd-MOFs prepared in Example 1 (13.4 mg, 0.01 mmol), and 2 mL of acetonitrile (MeCN) were stirred under visible light (>400 nm) for 8 hours. Prior to light irradiation, the glass reactor was vacuum-treated and backfilled with high-purity CO2 at 1 atm. The reaction mixture was dried using a rotary evaporator and purified by silica gel column chromatography (PE / ethyl acetate = 10:1) to afford compounds 1b-6b.

[0058] Product NMR:

[0059] The product was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4) to give yellow oil (94.9 mg, 99%). 1 H NMR (500MHz, CDCl3) δ7.42–7.26(m,5H),4.78–4.71(m,1H),4.48(s,2H),4.26(dd,J=5.2,2.2Hz,1H),4.08–3.99(m,2H).

[0060] Taking the catalytic preparation of compound 1b as an example, the yield using Cd-MOF photocatalysis is 19%; the yield using CdS photocatalysis is 25.2%.

[0061] The product was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.3) to give yellow oil (94.9 mg, 99%). 1 H NMR(500 MHz, CDCl3)δ7.20–7.12(m,2H),6.88–6.81(m,2H),4.67(dd,J=5.6,2.7Hz,1H) ,4.36(s,2H),4.22–4.16(m,1H),3.97(t,J=2.4Hz,2H),3.76(d,J=4.9Hz,3H).

[0062] The product was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4) to give yellow oil (94.9 mg, 99%). 1 H NMR (500MHz, CDCl3) δ7.33–7.22(m,2H),7.07–6.97(m,2H),4.72(dd,J=5.7, 2.7Hz, 1H), 4.43 (s, 2H), 4.25 (dt, J = 3.1, 2.2Hz, 1H), 4.02 (t, J = 2.4Hz, 2H).

[0063] The product was purified by silica gel column chromatography (PE / ethyl acetate = 5:1, Rf = 0.3) to give yellow oil (94.9 mg, 99%). 1 H NMR(500MHz, CDCl3)δ4.73(d,J=2.9Hz,1H),4.33–4.21(m,1H),4.16(t,J=2.4Hz,2 H),3.12(t,J=7.0Hz,2H),1.83–1.36(m,5H),1.35–1.11(m,4H),1.07–0.91(m,1H).

[0064] The product was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.5) to give a yellowish yellow (94.9 mg, 99%). 1H NMR (500 MHz, CDCl3) δ7.40–7.31 (m, 5H), 5.30–5.22 (m, 1H), 4.71 (dd, J = 5.6, 2.7 Hz, 1H), 4.21 (dt, J = 3.0, 2.2 Hz, 1H), 4.10 (dt, J = 14.2, 2.4 Hz, 1H), 3.77 (dt, J = 14.2, 2.4 Hz, 1H), 1.60 (d, J = 7.1 Hz, 3H). Cyclic stability experiment

[0065] Taking the preparation of compound 1b as an example, after the reaction was complete, the recovered catalyst was washed with acetone (6 mL x 3), air-dried, and reused in a continuous run. The results, as shown in Figure 1, show high catalytic efficiency even after nine cycles.

[0066] The above is a detailed description of the embodiments of the present application, but the present application is not limited to the above embodiments. Various changes can be made within the scope of knowledge possessed by ordinary technicians in the relevant technical field without departing from the scope of protection of the present application.

Claims

1. A MOFs composite material, characterized in that: The invention comprises Cd-MOF and CdS; the Cd metal cluster in the Cd-MOF is connected to one end of cysteamine, and the other end of the cysteamine is connected to CdS.

2. The MOFs composite material according to claim 1, characterized in that: The Cd-MOF is prepared from a ligand and a cadmium salt by a solvothermal method; Wherein, the structural formula of the ligand is as follows:

3. A method for preparing the MOFs composite material according to claim 1 or 2, characterized in that: The steps include: S1: heating Cd-MOF, cysteamine and solvent to obtain an intermediate; S2: Add cadmium salt and thioacetamide in step S1 and continue the reaction to obtain the product.

4. The preparation method according to claim 3, characterized in that: In step S1, the temperature of the heating reaction is 60°C to 100°C.

5. The preparation method according to claim 3, characterized in that: In step S1, the molar ratio of Cd-MOF to cysteamine is (3-6):

1.

6. The preparation method according to claim 3, characterized in that: The solvent is selected from at least one of ethanol, methanol, ethyl acetate, water and DMF.

7. The preparation method according to claim 3, characterized in that: The Cd-MOF is prepared by the following method: The ligand, cadmium salt and organic solvent are mixed to undergo a solvothermal reaction to obtain Cd-MOF.

8. The preparation method according to claim 7, characterized in that: The temperature of the solvothermal reaction is 90°C to 150°C.

9. The preparation method according to claim 7, characterized in that: The solvent thermal reaction time is 12h to 84h.

10. Use of the MOFs composite material as claimed in claim 1 or 2 in the photocatalytic cyclization reaction of propargylamine and CO2.

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