CN117551352B - A MOFs composite material and its preparation method and application - Google Patents
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Abstract
本发明公开了一种MOFs复合材料及其制备方法和应用，其包括Cd‑MOF和CdS；所述Cd‑MOF中的Cd金属簇与半胱胺的一端连接，所述半胱胺的另一端与CdS连接。本发明的MOFs复合材料对催化CO2与炔丙胺环化反应具有出色稳定性和催化效率性能。这是因为Cd‑MOF中的金属簇与半胱胺的一端连接，半胱胺的另一端与CdS连接，CdS和Cd‑MOF的协同作用极大的提升了催化CO2与炔丙胺环化反应。
The present invention discloses a MOFs composite material and a preparation method and application thereof, which includes 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 MOFs composite material of the present invention has excellent stability and catalytic efficiency performance for catalyzing the cyclization reaction of CO 2 and propargylamine. This is because the metal cluster in Cd-MOF is connected to one end of cysteamine, and the other end of cysteamine is connected to CdS, and the synergistic effect of CdS and Cd-MOF greatly improves the catalytic cyclization reaction of CO 2 and propargylamine.
Description
Technical Field
The invention relates to the technical field of metal organic frame materials, in particular to a MOFs composite material and a preparation method and application thereof.
Background
In recent years, carbon neutralization has attracted considerable attention because carbon dioxide (CO 2) as a greenhouse gas causes environmental and climate problems. CO 2 is also a promising source of C 1 in synthetic chemistry, which is more environmentally friendly and safer than traditional sources of C 1 such as CO. Oxazolidinones have good bactericidal activity and low toxicity to humans and are often used as antibiotics in clinical medicine. Cyclization of propynylamine with CO 2 has become an effective method for synthesizing 2-oxazolidinones. However, in the CO 2 and propynylamine cyclization reaction system, CO 2 activation typically requires high temperature and pressure due to the kinetic inertness and thermodynamic stability of CO 2, which greatly reduces the recovery performance of the catalyst. Therefore, development of a photocatalyst which is mild in condition and does not contain noble metal is urgently required, and green conversion of carbon dioxide and propynylamine is a great challenge under normal temperature and pressure and illumination conditions.
Therefore, it is necessary to develop a catalyst which has high stability and high catalytic efficiency and can be used for photocatalytic cyclization of propargylamine with CO 2 at normal temperature and normal pressure.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the first aspect of the invention provides a MOFs composite material which has high cycle stability and high catalytic efficiency, and can be used for photocatalytic cyclization reaction of propargylamine and CO 2 at normal temperature and normal pressure.
The second aspect of the invention also provides a preparation method of the MOFs composite material.
The third aspect of the invention also provides an application of the MOFs composite material.
According to the MOFs composite material provided by the embodiment of the first aspect of the invention, the MOFs composite material comprises Cd-MOFs and CdS, wherein Cd metal clusters in the Cd-MOFs are connected with one end of cysteamine, and the other end of cysteamine is connected with CdS.
The MOFs composite material provided by the embodiment of the invention has at least the following beneficial effects:
The MOFs composite material has excellent stability and catalytic efficiency performance for catalyzing cyclization reaction of CO 2 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, and the synergistic effect of CdS and Cd-MOF greatly promotes the cyclization reaction of catalytic CO 2 and propargylamine.
According to some embodiments of the invention, the Cd-MOF is prepared from a ligand and a cadmium salt by a solvothermal method;
wherein the structural formula of the ligand is shown as follows:
According to a second aspect of the present invention, there is provided a method for preparing MOFs composite material, comprising the steps of:
s1, heating Cd-MOF, cysteamine and a solvent to react to obtain an intermediate;
s2, adding cadmium salt and thioacetamide in the step S1 for continuous reaction, and obtaining the catalyst.
According to some embodiments of the invention, in step S1, the temperature of the heating reaction is 60 to 100 ℃.
According to some embodiments of the invention, in step S1, the molar ratio of Cd-MOF to cysteamine is (3-6): 1.
According to some embodiments of the invention, in step S2, the molar ratio of the cadmium salt to the thioacetamide is (0.5-2): 1.
According to some embodiments of the invention, the solvent is selected from at least one of ethanol, methanol, ethyl acetate, water, DMF.
According to some embodiments of the invention, the Cd-MOF is prepared by the following method:
and mixing the ligand, cadmium salt and an organic solvent for solvothermal reaction to obtain the Cd-MOF.
According to some embodiments of the invention, the solvothermal reaction temperature is 90-150 ℃.
According to some embodiments of the invention, the solvothermal reaction time is 12-84 hours.
According to some embodiments of the invention, the organic solvent is selected from at least one of dimethylformamide, ethanol, acetonitrile, ethyl acetate.
According to some embodiments of the invention, the cadmium salt includes at least one of cadmium nitrate, cadmium acetate.
The third aspect of the invention provides an application of MOFs composite material in photocatalysis of cyclization reaction of propargylamine and CO 2.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the cycling stability of MOFs composites prepared in example 1 of the present invention in photocatalytic propargylamine and carbon dioxide cyclization reactions.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Example 1 provides a MOFs composite material, the preparation method of which is as follows:
The synthesis of the ligand is as follows, and the preparation steps are as follows:
Step one A mixture of 2.97g of 3- (methoxycarbonyl) phenylboronic acid (16.5 mmol), 1.42g of 1,3,6, 8-tetrabromopyrene (2.75 mmol), 3.0g of potassium carbonate (22 mmol) and 40mL of dioxane was stirred under nitrogen at room temperature for 30min, followed by the addition of 0.05g 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 150mL of 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 give 1,3,6, 8-tetrakis (3-methoxycarbonylphenyl) pyrene in 76% yield.
Step two, 2.5g of 1,3,6, 8-tetrakis (3-methoxycarbonylphenyl) pyrene was dissolved in 160mL of THF, 160mL of an aqueous solution in which 10g of NaOH was dissolved was added with stirring, and the mixture was refluxed for 72 hours with stirring, and the organic solvent was removed in vacuo, and the mixture was filtered. The pH of the filtrate was adjusted to 1 with concentrated hydrochloric acid. The yellow solid obtained was collected by filtration, washed with water and methanol and dried in a vacuum oven to give the ligand (H 4 PTTB) in 98% yield. The hydrogen spectrum data are as follows:
1H 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.
synthesis of Cd-MOFs
H 4PTTB(69mg,0.1mmol)、Cd(NO3)2·4H2 O (206 mg,0.667 mmol), dimethylformamide (DMF, 3.5 mL) and H 2 O (1 mL) were placed in a glass vial, sealed and heated to 100℃in an oven. After 72H, orange blocky crystals (82.4 mg, 87.6% yield based on H 4 PTTB) were obtained and air dried.
MOFs composite material
S1, suspending 120mg of activated Cd-MOFs in 60mL of absolute ethanol. 120mg of cysteamine is added into the suspension, and the mixture is heated and stirred and refluxed for 1h at 80 ℃;
s2, 132.6mg of Cd (CH 3COO)2·2H2 O and 37.2mg of thioacetamide) is added, reflux is carried out for 12 hours, and the MOFs composite material (named as CdS@Cd-MOFs) obtained by centrifugation is washed 2 times in deionized water and dried at 60 ℃.
Test example 1
The MOFs composite material prepared in example 1 is used for catalyzing the cyclisation reaction of propargylamine and CO 2, and is specifically as follows:
Preparation of propargylamine compounds
The reaction general formula and the preparation steps are as follows:
3-bromopropyne (4 mmol) was added dropwise via a constant pressure dropping funnel to a 25mL glass bottle of the amine-based compound (20 mmol) under stirring at room temperature for 12 hours under magnetic stirring, and after completion of the reaction, the reaction solution was diluted with Et 2 O and washed with saturated aqueous NaHCO 3 (3X 25 mL). The extracted organic phase was concentrated by rotary evaporation and purified by column chromatography on silica gel (PE: ea=10:1) to give the product as a yellow oil.
Propargylamine compounds 1 a-6 a are prepared by the preparation method.
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate) ＝10:1,Rf＝0.5),1H 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).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate) ＝10:1,Rf＝0.4).1H 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).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate) ＝10:1,Rf＝0.6).1H 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).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate) ＝10:1,Rf＝0.6).1H 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).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate) ＝10:1,Rf＝0.4).1H 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).
Cyclization of propynylamine with CO 2:
Propargylamine compound 1 a-7 a, 1, 3-tetramethylguanidine (TMG, 11.5mg,0.1 mmol), cdS@Cd-MOFs (13.4 mg,0.01 mmol) prepared in example 1, and 2mL of acetonitrile (MeCN) prepared above were each stirred under visible light (> 400 nm) for 8 hours. Before light irradiation, the glass reactor is subjected to vacuum treatment and backfilled with high-purity CO 2 under the pressure of 1atm, the reaction mixture is dried by spin-drying with a rotary evaporator, and the yellow oily matter (PE/ethyl acetate=10:1) is obtained by purification with silica gel column chromatography, so that the compounds 1 b-6 b are obtained.
Product nuclear magnetism:
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.4) gives butter (94.9mg,99％).1H 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).
Taking the catalysis to prepare the compound 1b as an example, the yield of the photocatalysis by Cd-MOF is 19 percent, and the yield of the photocatalysis by CdS is 25.2 percent.
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.3) gives butter (94.9mg,99％)..1H NMR(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).
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.4) gives butter (94.9mg,99％)..1H 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).
Purification by silica gel column chromatography (PE/ethyl acetate=5:1, rf=0.3) gives butter (94.9mg,99％).1H NMR(500MHz,CDCl3)δ4.73(d,J＝2.9Hz,1H),4.33–4.21(m,1H),4.16(t,J＝2.4Hz,2H),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).
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.5) gives butter (94.9mg,99％)..1H NMR(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).
Cycling stability experiment
Taking the preparation of compound 1b as an example, after completion of the reaction, the recovered catalyst was washed with acetone (6 ml×3), dried in air, and reused in continuous operation. The results are shown in FIG. 1, and the catalyst has high catalytic efficiency after nine cycles.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. The MOFs composite material is characterized by comprising Cd-MOF and CdS, wherein a Cd metal cluster in the Cd-MOF is connected with one end of cysteamine, and the other end of cysteamine is connected with CdS;
the Cd-MOF is prepared from a ligand and cadmium salt by a solvothermal method;
wherein the structural formula of the ligand is shown as follows:
。
2. The method for preparing MOFs composite according to claim 1, comprising the steps of:
s1, heating Cd-MOF, cysteamine and a solvent to react to obtain an intermediate;
s2, adding cadmium salt and thioacetamide in the step S1 for continuous reaction, and obtaining the catalyst.
3. The preparation method of MOFs composite materials according to claim 2, wherein in step S1, the heating reaction temperature is 60-100 ℃.
4. The method of preparing MOFs composite according to claim 2, wherein in step S1, the molar ratio of Cd-MOF to cysteamine is (3-6): 1.
5. The method for preparing MOFs composite according to claim 2, wherein the solvent is at least one selected from ethanol, methanol, ethyl acetate, water, DMF.
6. The method for preparing MOFs composite according to claim 2, wherein the Cd-MOF is prepared by:
and mixing the ligand, cadmium salt and an organic solvent for solvothermal reaction to obtain the Cd-MOF.
7. The preparation method of MOFs composite materials according to claim 2, wherein the solvothermal reaction temperature is 90-150 ℃.
8. The preparation method of MOFs composite materials according to claim 2, wherein the solvothermal reaction time is 12-84 hours.
9. Use of the MOFs composite according to claim 1 for photocatalytic cyclisation of propargylamine with CO 2.
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