A MOFs composite material and its preparation method and application

Abstract

This invention discloses a MOF composite material, its preparation method, and its applications, 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. The MOF composite material of this invention exhibits excellent stability and catalytic efficiency in the cyclization reaction of CO2 and propargylamine. This is because the 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 synergistic effect of CdS and Cd-MOF greatly enhances the catalytic cyclization reaction of CO2 and propargylamine.

Description

Technical Field

[0001] The present invention 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 promising C1 source in synthetic chemistry, which is more environmentally friendly and safer than traditional C1 sources such as CO. Oxazolidinones have good bactericidal activity and low toxicity to the human body, and are often used as antibiotics in clinical medicine. The cyclization reaction of propargylamine with CO2 has become an effective method for the synthesis of 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, it is urgent to develop photocatalysts with mild conditions and no precious metals. It is a huge challenge to achieve the green conversion of carbon dioxide and propargylamine under normal temperature and pressure and light conditions.

[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. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the first aspect of the present invention provides a MOFs composite material with high cycle stability and high catalytic efficiency, which can photocatalyze the cyclization reaction of propargylamine with CO2 at room temperature and pressure.

[0005] The second aspect of the present invention also provides a method for preparing a MOFs composite material.

[0006] The third aspect of the present invention also provides an application of a MOFs composite material.

[0007] According to the first aspect of the present invention, an embodiment provides a MOFs composite material, 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.

[0008] The MOFs composite material according to the embodiment of the present invention has at least the following beneficial effects:

[0009] The MOFs composite material of the present invention has excellent stability and catalytic efficiency in catalyzing the cyclization reaction of CO2 and 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 improves the catalytic cyclization reaction of CO2 and propargylamine.

[0010] According to some embodiments of the present invention, the Cd-MOF is prepared from a ligand and a cadmium salt by a solvothermal method;

[0011] Wherein, the structural formula of the ligand is as follows:

[0012]

[0013] According to the second aspect of the present invention, 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, adding cadmium salt and thioacetamide in step S1 and continuing the reaction to obtain.

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

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

[0018] According to some embodiments of the present invention, 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 invention, the solvent is selected from at least one of ethanol, methanol, ethyl acetate, water, and DMF.

[0020] According to some embodiments of the present invention, 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 invention, the temperature of the solvothermal reaction is 90-150°C.

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

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

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

[0026] A third aspect of the present invention 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 invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0031] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0032] Example 1

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

[0034] Synthesis of ligands: The reaction equation is as follows, and the preparation steps are as follows:

[0035]

[0036] Step 1: At room temperature, 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 in nitrogen for 30 min, and then 0.05 g of tetrakis(triphenylphosphine)palladium (0.045 mmol) was added. The reaction mixture was refluxed for 3 days. After cooling to room temperature, the reaction mixture was poured into 150 mL of an aqueous solution containing concentrated hydrochloric acid (3:1). The yellow suspension solution was extracted with chloroform (100 mL×3), the organic phases were combined, and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator under vacuum to obtain 1,3,6,8-tetrakis(3-methoxycarbonylphenyl)pyrene with a yield of 76%.

[0037] Step 2: Dissolve 2.5 g of 1,3,6,8-tetrakis(3-methoxycarbonylphenyl)pyrene in 160 mL of THF, and add 160 mL of 10 g of NaOH aqueous solution while stirring, stir and reflux for 72 h, remove the organic solvent in vacuo, and filter the mixture. Adjust the pH value of the filtrate to 1 with concentrated hydrochloric acid. Collect the obtained yellow solid by filtration, wash with water and methanol, and dry in a vacuum oven to obtain the ligand (H4PTTB), with a yield of 98%. The hydrogen spectrum data are as follows:

[0038] 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 .

[0039] Synthesis of Cd-MOFs

[0040] 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 glass vial, sealed and heated to 100°C in an oven. After 72 h, orange block crystals (82.4 mg, 87.6% yield based on H4PTTB) were obtained and air-dried.

[0041] MOFs Composites

[0042] S1. Suspend 120 mg of activated Cd-MOFs in 60 mL of anhydrous ethanol. Add 120 mg of cysteamine to the suspension, heat and stir, and reflux at 80 °C for 1 h.

[0043] S2. Add 132.6 mg Cd(CH3COO)2·2H2O and 37.2 mg thioacetamide, and reflux for 12 h. The MOFs composite material (named: CdS@Cd-MOFs) obtained by centrifugation was washed twice in deionized water and dried at 60°C.

[0044] Test Example 1

[0045] The MOFs composite material prepared in Example 1 was used to catalyze the cyclization reaction of propargylamine and CO2, as follows:

[0046] Preparation of propargylamine compounds

[0047] The general reaction formula and preparation steps are as follows:

[0048]

[0049] Under stirring at room temperature, 3-bromopropyne (4 mmol) was added dropwise to a 25 mL glass bottle of an amino compound (20 mmol) through a constant pressure dropping funnel within 30 minutes and magnetically stirred for 12 hours. After the reaction was completed, the reaction solution was diluted with Et2O and washed with a saturated aqueous NaHCO3 solution (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 to 6a were prepared by the above preparation method.

[0051]

[0052] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.5), 1H NMR (500 MHz, CDCl3) δ 7.42–7.26 (m, 5H), 3.88 (s, 2H), 3.42 (d, J = 2.2 Hz, 2H), 2.28 (t, J = 2.1 Hz, 1H), 1.68 (s, 1H).

[0053]

[0054] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4). 1H NMR (500 MHz, CDCl3) δ 7.29 (dd, J = 6.0, 2.4 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 3.84 (d, J = 2.2 Hz, 2H), 3.81 (d, J = 2.6 Hz, 3H), 3.43 (t, J = 2.5 Hz, 2H), 2.28 (d, J = 2.4 Hz, 1H), 1.75 (d, J = 16.0 Hz, 1H).

[0055]

[0056] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.6). 1H NMR (500 MHz, CDCl3) δ 7.33 (dt, J = 8.3, 4.2 Hz, 2H), 7.07–6.94 (m, 2H), 3.87 (s, 2H), 3.43 (t, J = 4.1 Hz, 2H), 2.29 (t, J = 2.4 Hz, 1H), 1.70 (s, 1H).

[0057]

[0058] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.6). 1H NMR (500 MHz, CDCl3) δ 3.40 (d, J = 2.4 Hz, 2H), 2.50 (d, J = 6.7 Hz, 2H), 2.19 (s, 1H), 1.70 (d, J = 15.5 Hz, 5H), 1.44 (dd, J = 6.6, 3.3 Hz, 2H), 1.30–1.09 (m, 3H), 1.01–0.85 (m, 2H).

[0059]

[0060] The yellow oil was purified by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4). 1H NMR (500 MHz, CDCl3) δ 7.40–7.24 (m, 5H), 4.02 (q, J = 6.6 Hz, 1H), 3.36 (dd, J = 17.1, 2.5 Hz, 1H), 3.16 (dd, J = 17.1, 2.4 Hz, 1H), 2.22 (t, J = 2.4 Hz, 1H), 1.37 (d, J = 6.6 Hz, 3H).

[0061] Cyclization reaction of propargylamine with CO2:

[0062] The propargylamine compounds 1a-7a 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 for 8 hours under visible light (>400 nm). Before light irradiation, the glass reactor was vacuum treated and backfilled with high-purity CO2 at a pressure of 1 atm; the reaction mixture was dried by rotary evaporator and purified by silica gel column chromatography to obtain a yellow oil (PE / ethyl acetate = 10:1), thereby obtaining compounds 1b-6b.

[0063] Product NMR:

[0064]

[0065] 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).

[0066] 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%.

[0067]

[0068] Purification by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.3) gave yellow oil (94.9 mg, 99%). 1 HNMR (500MHz, 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).

[0069]

[0070] Purification by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.4) gave yellow oil (94.9 mg, 99%). 1HNMR(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).

[0071]

[0072] 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).

[0073]

[0074] Purification by silica gel column chromatography (PE / ethyl acetate = 10:1, Rf = 0.5) gave yellow oil (94.9 mg, 99%). 1 HNMR (500MHz, CDCl3) δ7.40–7.31(m,5H),5.30–5.22(m,1H),4.71(dd,J=5.6,2.7Hz,1H),4.21(dt,J =3.0,2.2Hz,1H),4.10(dt,J=14.2,2.4Hz,1H),3.77(dt,J=14.2,2.4Hz,1H),1.60(d,J=7.1Hz,3H).

[0075] Cyclic stability test

[0076] Taking the preparation of compound 1b as an example, after the reaction was completed, the recovered catalyst was washed with acetone (6 mL×3), dried in air, and reused in continuous operation. Figure 1 As shown, the catalytic efficiency is still high after nine cycles.

[0077] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

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

3. The method for preparing the MOFs composite material according to claim 2, characterized in that: In step S1, the temperature of the heating reaction is 60-100°C.

4. The method for preparing the MOFs composite material according to claim 2, characterized in that: In step S1, the molar ratio of Cd-MOF to cysteamine is (3-6):

1.

5. The method for preparing the MOFs composite material according to claim 2, characterized in that: The solvent is selected from at least one of ethanol, methanol, ethyl acetate, water and DMF.

6. The method for preparing the MOFs composite material according to claim 2, 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.

7. The method for preparing the MOFs composite material according to claim 2, characterized in that: The temperature of the solvent thermal reaction is 90-150°C.

8. The method for preparing the MOFs composite material according to claim 2, characterized in that: The solvent thermal reaction time is 12 to 84 hours.

9. Use of the MOFs composite material according to claim 1 in the photocatalytic cyclization reaction of propargylamine and CO2.

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