CN110116024B - Heterogeneous three-dimensional double-valence Cu-MOF catalyst and preparation method and application thereof - Google Patents

Heterogeneous three-dimensional double-valence Cu-MOF catalyst and preparation method and application thereof Download PDF

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CN110116024B
CN110116024B CN201910508560.0A CN201910508560A CN110116024B CN 110116024 B CN110116024 B CN 110116024B CN 201910508560 A CN201910508560 A CN 201910508560A CN 110116024 B CN110116024 B CN 110116024B
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赵斌
姜晓蕾
侯胜利
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Abstract

A heterogeneous three-dimensional double-valence Cu-MOF catalyst and a preparation method and application thereof belong to the field of catalyst synthesis and application. Under the solvothermal condition, adding a small amount of formic acid into a mixed solvent of DMA and acetonitrile by using an organic ligand 5-aminonicotinic acid, copper nitrate pentahydrate and cuprous iodide to carry out solvothermal reaction to obtain Cu constructed by the 5-aminonicotinic acidI 6I5‑CuII 2Double valence MOF material { [ Cu ]9I5L6·3DMA]·(NO3)·9DMA}n. The MOF material has positive charges, has a three-dimensional stp topological structure, has the advantages of cheap and easily-obtained raw materials, simple preparation process, high porosity of the obtained material, large specific surface area and the like, not only contains two copper ions with different valence states simultaneously, but also has a large number of uncoordinated naked amino groups on a ligand, and can be used for synergistically catalyzing terminal alkynylamine and CO2The catalytic activity of the catalyst can still keep higher level after being recycled for many times.

Description

Heterogeneous three-dimensional double-valence Cu-MOF catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysis of crystalline materials, and technically relates to a preparation method of a bivalent Cu-MOF catalyst material constructed based on 5-aminonicotinic acid and a method for catalyzing alkynylamine and CO by using the same2Application of the reaction.
Background
The 2-oxazolidinone compound is an important chemical intermediate, and has important application value in the fields of material science, pesticide and medicine, for example, the 2-oxazolidinone compound is an intermediate of carmustine, lomustine and lomustine, and is a novel chemically synthesized antibacterial agent following sulfonamides and fluoroquinolones. Among the methods for synthesizing 2-oxazolidinones, carboxylation cyclization reaction using an alkynylamine compound and carbon dioxide is one of the greenest methods. The carbon dioxide which is a green, cheap and easily available C1 resource can be utilized, and the atom utilization rate can reach 100%. However, due to the chemical inertness and thermal stability of carbon dioxide, catalysis of such reactions is usually carried out at high temperatures and pressures in the presence of noble metal catalysts such as palladium, platinum, gold, silver, etc., and requires the addition of a base as a promoter. Therefore, the method for constructing the high-efficiency non-noble metal catalyst and catalytically synthesizing the 2-oxazolidone compound under the mild condition without the existence of the cocatalyst has very important industrial value and research significance.
Metal Organic Frameworks (MOFs) are a class of organic/inorganic hybrid materials with porous structures constructed by central metal ions and organic ligands through coordination bonds. Due to the characteristics of high dispersity of catalytic active sites, easy modification of a framework structure, adjustability of pore channel size and the like, the catalyst is widely applied to catalytic hydrogenation, hydration, coupling, cyclization and other reactions. Among the reported metal organic framework catalysts, the catalytic conversion of carbon dioxide using copper, an inexpensive metal, has attracted much attention.
Disclosure of Invention
The invention aims to overcome the defects of the current alkynylamine compounds and CO2The deficiency of cycloaddition reaction, 5-amino nicotinic acid is taken as a ligand, copper iodine cluster and binuclear copper are taken as two different nodes, the preparation method of the novel heterogeneous double valence Cu-MOF catalyst and the application thereof in catalyzing CO2And an application of synthesizing 2-oxazolidone products by using the alkynylamine compounds.
The technical scheme of the invention is as follows:
the invention relates to a heterogeneous three-dimensional divalent Cu-MOF catalyst which is characterized by having a chemical formula of { [ Cu ]9I5L6·3DMA]·(NO3)·9DMA}nWherein L is organic ligand 5-amino nicotinic acid, DMA is N, N-dimethyl acetamide. The framework structure contains copper ions with two different valence states, namely monovalent copper CuIAnd divalent copper CuIIIn which every six CuIRespectively connected with five iodide ions to form olive-shaped [ Cu ]6I5]+And a cation cluster, and taking the cluster as a core to coordinate with six pyridine N atoms of six ligands. Each ligand is coordinated with two adjacent bivalent copper ions through a carboxyl group at the other end to form a typical Paddle-wheel binuclear copper structure. The binuclear copper ends are respectively coordinated with two oxygen atoms from DMA molecules, and each divalent copper is in a coordination mode of penta-coordination. Finally forming a three-dimensional long-range ordered structure. Six [ Cu ] viewed from the c-axis6I5]+The cluster and six Paddle-wheel binuclear copper surround a diameter of
Figure BDA0002092643210000021
The duct of (2). As the inner wall of the pore channel has rich exposed amino sites, alkalinity can be provided during the catalytic reaction, so that additional alkali does not need to be added as a cocatalyst.
A preparation method of a heterogeneous three-dimensional double-valence Cu-MOF catalyst based on 5-aminonicotinic acid comprises the following steps:
(1) synthesis of Cu-MOF: feeding an organic ligand L (5-aminonicotinic acid), copper nitrate pentahydrate and cuprous iodide according to a molar ratio of 4:2:1, wherein each 0.054 mmol of copper nitrate pentahydrate corresponds to 3 mL-4mL of N, N-dimethylacetamide, 2mL-3mL of acetonitrile and 20 muL-40 muL of anhydrous formic acid, uniformly mixing the reactants and a solvent, placing the mixture in an oven at 120 ℃ under a closed condition for constant-temperature reaction for 72 hours, then slowly cooling to room temperature at a speed of 1.25 ℃ per hour, and adding a small amount of formic acid into a mixed solvent of N, N-dimethylacetamide and acetonitrile for solvothermal reaction to obtain a green hexagonal crystal;
(2) post-treatment of Cu-MOF: and (2) centrifuging the crystals obtained in the step (1), washing the crystals with N, N-dimethylacetamide and acetonitrile solution, activating the crystals for 2 days by using acetonitrile, replacing new acetonitrile solution every 8h, and drying the crystals at 60 ℃ for 6h to obtain green crystals, namely the Cu-MOF catalyst.
The preferable conditions in the step (1) are as follows: the 5-aminonicotinic acid, copper nitrate pentahydrate and cuprous iodide are mixed uniformly according to the mol ratio of 4:2:1, and the copper nitrate pentahydrate of 0.054 millimole corresponds to 3mL of N, N-dimethylacetamide, 2mL of acetonitrile solution and 25 muL of anhydrous formic acid, and then the mixture is sealed and reacted for 3 days at 120 ℃.
The heterogeneous Cu-MOF catalyst synthesized by the method is used for catalyzing terminal alkynylamine and CO2The 2-oxazolidone compound is prepared by cycloaddition reaction, and after the reaction is completed, the Cu-MOF catalyst can be repeatedly used and the catalytic activity of the Cu-MOF catalyst is not obviously reduced。
The invention has the advantages and beneficial effects that:
the catalyst has high chemical stability and thermal stability, the thermal stability of the catalyst can reach 250 ℃, the chemical stability is realized, the structure can still be kept unchanged after five times of catalytic cycle, and the powder diffraction peak can still be consistent with the original powder diffraction peak after the catalyst is soaked in various common solvents. The heterogeneous Cu-MOF catalyst has a diameter of C-axis
Figure BDA0002092643210000031
The inner wall of the pore canal has high-density uncoordinated amino groups with alkalinity, and the Cu-MOF catalyst simultaneously has copper ions with two different valence states of monovalent copper and divalent copper, so the heterogeneous Cu-MOF catalyst catalyzes terminal alkynylamine and CO under the condition of no cocatalyst and no solvent2The reaction for generating the 2-oxazolidone compound has high catalytic activity.
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The invention is further described with reference to the following figures and examples, which are intended to give specific reference thereto without limiting the scope of the invention.
FIG. 1 is a diagram of the coordination pattern of the heterogeneous Cu-MOF catalyst.
FIG. 2 is a schematic representation of the three-dimensional structure of the heterogeneous Cu-MOF catalyst.
Fig. 3 is a graph of the original thermogram and the thermogram after 5 catalytic cycles of the heterogeneous Cu-MOF catalyst.
Figure 4 is an X-ray powder diffraction (XRD) pattern after catalytic cycling of the heterogeneous Cu-MOF catalyst.
FIG. 5 shows that the heterogeneous Cu-MOF catalyst catalyzes the terminal alkynylamine and CO2The catalytic cycle results of the reaction to produce 2-oxazolidone compounds.
Detailed Description
Heterogeneous Cu-MOF catalyst
A heterogeneous three-dimensional double-valence Cu-MOF catalyst based on 5-aminonicotinic acid has a chemical formula of { [ Cu ]9I5L6·3DMA]·(NO3)·9DMA}nWherein L is organic ligand 5-amino nicotinic acid, DMA is N, N-dimethyl acetamide; s is solvent molecule in the pore channel. The framework structure contains copper ions with two different valence states, namely monovalent copper CuIAnd divalent copper CuIIIn which every six CuIRespectively connected with five iodide ions to form olive-shaped [ Cu ]6I5]+And a cation cluster, and taking the cluster as a core to coordinate with six pyridine N atoms of six ligands. Each ligand is coordinated with two adjacent bivalent copper ions through a carboxyl group at the other end to form a typical Paddle-wheel binuclear copper structure. The binuclear copper ends are respectively coordinated with two oxygen atoms from DMA molecules, and each divalent copper is in a penta-coordinated coordination mode. Finally forming a three-dimensional long-range ordered structure. Six [ Cu ] viewed from the c-axis6I5]+The cluster and six Paddle-wheel binuclear copper surround a diameter of
Figure BDA0002092643210000041
The duct of (2).
The obtained crystal structure belongs to a hexagonal crystal system, P6/m space group and the unit cell parameters are as follows: 24.4751(4), 24.4751(4), 23.8686(4), α 90 °, β 90 °, γ 120 °.
Bis, heterogeneous Cu-MOF catalyst { [ (NO)3)·(CuI 6I5)(L)6(CuII 2)1.5·3(DMA)]·xS}nSynthesis and characterization of
Example 1:
sequentially adding 4mLN, N-dimethylacetamide, 2mL acetonitrile and 25 mu L anhydrous formic acid into copper nitrate pentahydrate (0.05mmol), cuprous iodide (0.1mmol) and organic ligand 5-aminonicotinic acid (0.2mmol), uniformly stirring, placing into a 120 ℃ oven, reacting at constant temperature for 72h, and naturally cooling to room temperature; the reaction solution was removed by centrifugation, washed three times with N, N-dimethylacetamide and acetonitrile respectively, activated for 2 days with acetonitrile and replaced with a new acetonitrile solution every 8 h. Removing the upper acetonitrile solution after centrifugation, and drying the precipitate in a 60 ℃ oven for 6h to obtain green powder, namely the Cu-MOF heterogeneous catalyst.
Example 2:
adding a mixed solution of 3mLN, N-dimethylacetamide and 2mL acetonitrile mixed with copper nitrate pentahydrate (0.2mmol) into cuprous iodide (0.05mmol) and organic ligand 5-aminonicotinic acid (0.1mmol), dropwise adding 40 muL of anhydrous formic acid into the mixed solution, uniformly stirring, placing into a 120 ℃ oven, reacting at constant temperature for 72h, and cooling to room temperature at the speed of 1.25 ℃ per hour; the reaction solution was removed by centrifugation, washed three times with N, N-dimethylacetamide and acetonitrile respectively, activated for 2 days with acetonitrile and replaced with a new acetonitrile solution every 8 h. Removing the upper acetonitrile solution after centrifugation, and drying the precipitate in a 60 ℃ oven for 6h to obtain green powder, namely the Cu-MOF heterogeneous catalyst.
Example 3:
sequentially adding 3mLN, N-dimethylacetamide, 2mL acetonitrile and 30 mu L anhydrous formic acid into copper nitrate pentahydrate (0.05mmol), cuprous iodide (0.1mmol) and organic ligand 5-aminonicotinic acid (0.2mmol), uniformly stirring, placing into a 120 ℃ oven, reacting at constant temperature for 72h, and naturally cooling to room temperature; the reaction solution was removed by centrifugation, washed three times with N, N-dimethylacetamide and acetonitrile respectively, activated for 2 days with acetonitrile and replaced with a new acetonitrile solution every 8 h. Removing the upper acetonitrile solution after centrifugation, and drying the precipitate in a 60 ℃ oven for 6h to obtain green powder, namely the Cu-MOF heterogeneous catalyst.
Three, heterogeneous Cu-MOF catalyst catalyzes reaction of alkynylamine and carbon dioxide
Placing 20mg of the synthesized Cu-MOF heterogeneous catalyst in a 20ml reaction tube with a branch, adding 1.32mmol of 2-methyl-3-butyl-2-amine, adding magnetons, and filling CO into the mouth of the reaction tube with the branch2Placing the packed test tube in a water bath at the temperature of 30 ℃ and stirring at constant temperature for reaction for 5 hours, weighing 0.25mmol of the internal standard substance 1,3, 5-trimethoxybenzene after the reaction is finished, adding the internal standard substance into the test tube, and adding 1ml of dichloromethane to fully dissolve the internal standard substance; after the reaction, the mixture was centrifuged by a dropper, and the supernatant was analyzed by nuclear magnetic resonance. And washing the reacted Cu-MOF catalyst with acetonitrile for three times, putting the washed Cu-MOF catalyst into an oven for drying at 60 ℃, and using the catalyst for next recycling. 2-methyl-3-butyl-2-amine withCO2The equation for the reaction is as follows:
Figure BDA0002092643210000061
in the above-mentioned reaction of 2-methyl-3-butyl-2-amine with CO2The yield of oxazolidinone in the reaction of (1) was as high as 99%.
As can be seen from FIGS. 1 and 2, the Cu-MOF heterogeneous catalyst contains a large number of uncoordinated amino groups. From FIG. 3, it can be seen that the Cu-MOF heterogeneous catalyst has high thermal stability.
As can be seen from FIGS. 3 and 4, the thermogravimetric and powder diffraction data of the Cu-MOF heterogeneous catalyst are not obviously changed after 5 times of reactions of cyclic use, which shows that the catalyst has good stability and can be recycled.
As can be seen from FIG. 5, the catalyst has good recycling performance, and the catalytic yield can still reach 88% after being reused for 5 times.
Table 1 below shows the catalysis of a series of terminal alkynylamines with CO over a Cu-MOF heterogeneous catalyst2Yield of the reaction. It can be found that the catalyst is generally applicable to various terminal alkynylamines and CO2The catalytic reaction of (1).
Table 1:
Figure BDA0002092643210000071
reaction conditions 1.32mmol of substrate, 20mg of Cu-MOF catalyst, 1atm CO25h, a-f, solvent-free and g, 50 mu l of triethylamine. Yields were based on 1,3, 5-trimethoxybenzene as internal standard to1H NMR nuclear magnetic calculation.
The foregoing is some of the preferred embodiments of the present invention, but the present invention should not be limited to the disclosure of this example. Therefore, equivalents and modifications may be made without departing from the spirit of the disclosure to fall within the scope of the invention. A few terms are necessary in the description and illustration, nor are they intended to be limiting of the invention.

Claims (5)

1. A heterogeneous three-dimensional double valence Cu-MOF catalyst is characterized in that the chemical formula is { [ Cu ]9I5L6·3DMA]·(NO3)·9DMA}nWherein L is an organic ligand 5-aminonicotinic acid; DMA is N, N-dimethylacetamide;
the crystal structure belongs to a hexagonal crystal system,P6/m space group, unit cell parameters are: a =24.4751(4), b =24.4751(4), c =23.8686(4), α =90 °, β =90 °, γ =120 °;
from the angle of the valence state of the central metal of the frame, the frame structure contains copper ions with two different valence states, namely monovalent copper CuIAnd divalent copper CuIIIn which every six CuIRespectively linked with five iodide ions to form [ Cu6I5]+Cluster of CuIAnd extend outwards through pyridine N atoms on the ligand, and simultaneously every two Cu atomsIIAnd is bridged with eight carboxyl oxygen from four ligands to form a typical Paddle-wheel binuclear copper structure, the binuclear copper ends are respectively coordinated with two oxygen atoms from DMA molecules, and each divalent copper is in a penta-coordinate coordination mode.
2. The heterogeneous three-dimensional divalent Cu-MOF catalyst according to claim 1, characterized in that it comprises a rugby-type [ Cu ]6I5]+The cationic cluster is used as a core to be coordinated with six pyridine N atoms of six ligands, each ligand is respectively coordinated with two adjacent divalent copper ions through carboxyl at the other end to form a typical Paddle-wheel binuclear copper structure, the tail end of the binuclear copper is respectively coordinated with two oxygen atoms from DMA molecules, each divalent copper is in a penta-coordinate coordination mode, and finally a three-dimensional long-range ordered structure is formed.
3. The heterogeneous three-dimensional divalent Cu-MOF catalyst according to claim 2, wherein [ Cu ] is oriented along the c-axis6I5]+The clusters are connected with Paddle-wheel binuclear copper and ligands to form a pore channel with about 15A, and the inner wall of the pore channel has high density of uncoordinated self-basicAmino group, and nitrate ion for maintaining charge balance and a large amount of free solvent molecules are contained in the channel.
4. A process for the preparation of a heterogeneous three-dimensional bimodal Cu-MOF catalyst according to any of claims 1 to 3, characterized in that it comprises the following steps: 1) under a closed condition, adding a small amount of formic acid into a mixed solvent of DMA and acetonitrile by an organic ligand 5-aminonicotinic acid, copper nitrate pentahydrate and cuprous iodide to obtain a crystal of a metal organic framework material through a solvothermal reaction; feeding an organic ligand 5-aminonicotinic acid, copper nitrate pentahydrate and cuprous iodide according to a molar ratio of 4:2:1, wherein each 0.054 millimole of copper nitrate pentahydrate corresponds to 3-4 mL of N, N-dimethylacetamide, 2-3 mL of acetonitrile and 20-40 muL of anhydrous formic acid; the solvothermal reaction temperature is 120 ℃, and the reaction time is 72 hours;
naturally cooling the obtained crystals of the metal organic framework material to room temperature or slowly cooling the crystals to the room temperature at the speed of 1.25 ℃ per hour;
and centrifuging the obtained crystals of the metal organic framework material, washing the crystals with N, N-dimethylacetamide and acetonitrile solution, activating the crystals for 2 days by using acetonitrile, replacing new acetonitrile solution every 8h, and drying the crystals at 60 ℃ for 6h to obtain green crystals, namely the Cu-MOF catalyst.
5. Use of the heterogeneous three-dimensional divalent Cu-MOF catalyst according to any of claims 1 to 3 for catalyzing alkynylamines with CO2The application of the 2-oxazolidone compound generated by cycloaddition reaction under the condition of no cocatalyst and no solvent.
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