CN111218006B - Nano-rod-shaped two-dimensional copper-based metal organic framework material, preparation method and application - Google Patents
Nano-rod-shaped two-dimensional copper-based metal organic framework material, preparation method and application Download PDFInfo
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Abstract
The invention relates to a preparation method of a nano-rod-shaped two-dimensional copper-based metal organic framework material, wherein the chemical molecular formula of the crystalline material is [ Cu (1H-1,2,4-triazole-1-acetic acid) ]2]nAnd n is an infinite alternating arrangement of the internal components of the material into the simplest molecular formula. The preparation method comprises the following steps: dispersing carboxylic acid organic ligand containing trinitrogen in an organic solvent and water to obtain turbid liquid; stirring the turbid solution under ultrasound and carrying out the stirring at room temperature; then adding a certain amount of copper nitrate, standing at a certain temperature for reaction, washing, separating and precipitating the reacted solution, and drying to obtain the precipitate, thus obtaining the two-dimensional material. The preparation method has simple and mild reaction conditions and is environment-friendly. The catalyst has good application prospect in organic catalytic reaction, especially hydrocarbon hydroxylation.
Description
Technical Field
The invention relates to a nanorod-shaped two-dimensional copper-based metal organic framework material formed by taking 1H-1,2,4-triazole-1-acetic acid as a ligand and taking transition metal copper as a metal center and a preparation method thereof, and the nanorod-shaped two-dimensional copper-based metal organic framework material has good catalytic performance on catalyzing hydrocarbon activation reaction due to the characteristic of large specific surface area.
Background
The metal organic framework material is a crystalline porous material which is formed by mutually linking metal ions and organic functional groups through covalent bonds or ion-covalent bonds and has a regular pore channel structure. Due to its high porosity and large specific surface area, reactants can be attached to the pores during the catalytic process, and the larger the specific surface area, the higher the conversion rate of the reaction. Meanwhile, the catalyst also has unsaturated metal sites, unsaturated metal sites are combined with water, ethanol and other small molecules to meet the coordination requirement, solvent molecules are removed after desolvation, a porous frame structure is reserved, and the unsaturated metal sites are exposed, so that molecules are more easily coordinated with the unsaturated metal sites, and the catalyst can be used for catalyzing hydrocarbon activation reaction, reducing the activation energy of the reaction and accelerating the reaction.
Disclosure of Invention
The invention provides a synthesis method of a nanorod-shaped two-dimensional copper-based metal organic framework material formed by coordination of 1H-1,2,4-triazole-1-acetic acid serving as a ligand and metal copper. The method comprises the following steps of,
weighing carboxylic acid organic ligand containing trinitrogen, and dispersing in an organic solvent and water to obtain turbid liquid; stirring the turbid solution under ultrasound and carrying out the stirring at room temperature; then adding a certain amount of copper nitrate, placing the mixture into a reaction kettle containing a polytetrafluoroethylene lining, reacting for 10-30h at a constant temperature of 50-100 ℃, and cooling to room temperature at a constant speed of 2-3 ℃/h to obtain purple crystals. And filtering and washing the obtained solution, then drying the solution in vacuum at 80 ℃ for 10-15h, and collecting a sample to obtain the crystal material.
The mol ratio of the organic ligand 1H-1,2,4-triazole-1-acetic acid to the copper nitrate is 0.5-1:1, and every 7mg of the organic ligand 1H-1,2,4-triazole-1-acetic acid corresponds to 2-4ml of N, N-dimethylformamide, 0.5-1.5ml of deionized water and 0.5-2ml of ethanol. As the optimum conditions, the molar ratio of the organic ligand 1H-1,2,4-triazole-1-acetic acid to copper nitrate was 0.6: 1, 2ml of N, N-dimethylformamide, 1.5ml of deionized water and 1ml of ethanol per 7mg of organic ligand 1H-1,2,4-triazole-1-acetic acid.
The room temperature referred to in the invention refers to the ambient temperature under normal pressure.
The crystal synthesized by the present invention was subjected to structure measurement using a small molecule type single crystal X-ray diffractometer of Rigaku corporation, japan, and data such as diffraction intensity and unit cell parameters were measured at 293K using Mo K α rays monochromated by a graphite monochromator, and the collected data was subjected to empirical absorption correction using a scanning technique, and the obtained result was analyzed by a direct method using the Shelxtl-97 program and corrected by a full matrix least square method. The crystallographic data obtained are shown in table 1.
The other technical scheme of the invention is to apply the crystalline material metal organic framework material as a catalytic material to catalyzing hydrocarbon hydroxylation reaction.
The active center of the nano-rod-shaped two-dimensional copper-based metal organic framework material is a central divalent copper ion which is in a plane four-coordination structure, and the upper and lower surface sites of the plane are not occupied and are active sites which can be used as the active center to catalyze the hydrocarbon hydroxylation reaction.
The uncoordinated divalent copper ion active center of the nanorod-shaped two-dimensional copper-based metal organic framework material can catalyze the carbon-sulfur coupling reaction of diaryl disulfide and the hydroxylation reaction of the ortho position of the diaryl disulfide. The catalyst catalyzes two-step reaction simultaneously, the reaction is realized by a one-pot method, and the synthesis of the target compound is synthesized in one pot.
The coordination of the nano-rod-shaped two-dimensional copper-based metal-organic framework material contains unsaturated divalent copper ions to form a chelate with an S atom on a substituent group, so that the hydroxylation of an ortho-position C-H bond on a diaryl disulfide is induced, and then the hydroxylation is coupled with iodobenzene to generate a target product.
Drawings
FIG. 1: is a coordination environment diagram of the nanorod-shaped two-dimensional copper-based metal-organic framework material synthesized in example 1.
FIG. 2: is a three-dimensional stacking diagram of the two-dimensional copper-based metal-organic framework material of the nanorod-shaped prepared in example 1.
FIG. 3: is the XRD spectrum of the two-dimensional copper-based metal organic framework material in the shape of a nano rod prepared in example 1.
FIG. 4: is a thermogravimetric spectrum of the nanorod-shaped two-dimensional copper-based metal-organic framework material prepared in example 1.
FIG. 5: is a scanning electron microscope image of the two-dimensional copper-based metal organic framework material in a nanorod shape prepared in example 1.
Detailed Description
Example 1
0.06mmol of 1H-1,2,4-triazole-1-acetic acid and 0.1mmol of Cu (NO) are weighed out3)2·3H2O, 2ml of N, N-Dimethylformamide (DMF), 1.5ml of deionized water and 1ml of ethanol are subjected to ultrasonic treatment for 15min and added into a stainless steel reaction kettle with a polytetrafluoroethylene lining, the mixture is subjected to constant temperature reaction at 85 ℃ for 24h, and the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, so that the purple crystal nanorod-shaped two-dimensional copper-based porous crystalline metal organic framework material, namely Cu-MOF, is obtained. (the chemical general formula is [ Cu (1H-1,2, 4-Triazol-1-acetic acid) ]2]n, n is positive infinity, and n only represents the structural feature that the crystalline material is constructed by the repeated appearance of the minimum unit, and is written in a general formula
Example 2
A process for the preparation of 5-chloro-2- (phenylthio) phenol comprising the following experimental steps:
at room temperature, adding p-chloro-disulfide compound 1a (1mmol), 3mL of DMSO (dimethyl sulfoxide) solvent, iodobenzene 2a (0.45mmol) and cesium carbonate (1mmol) into a reactor in sequence, stirring at room temperature to fully dissolve the p-chloro-disulfide compound, adding an MOF-Cu catalyst (0.10% mol), reacting at 80 ℃ for 8 hours, filtering out the MOF-Cu catalyst after TLC detection reaction is completed, pouring the reaction system into 30mL of water, extracting with 15mL of dichloromethane for three times, drying with anhydrous sodium sulfate, removing dichloromethane under reduced pressure, and performing column chromatography on the residue to obtain the target compound 3a with the yield of 89%.
1H NMR(400MHz,CDCl3)δ(ppm)7.47(d,J＝8.4Hz,1H,Ar-H),7.25–7.19(m,2H,Ar-H),7.19–7.14(m,1H,Ar-H),7.10–7.06(m,3H,Ar-H),6.94(dd,J＝8.4,2.4Hz,1H,Ar-H),6.56(s,2H,OH)；
13C NMR(100MHz,CDCl3)δ(ppm)157.8,137.7,137.5,131.2,129.3,126.9,126.4,121.7,116.0,115.0.
Example 3
A process for the preparation of 3-bromo-2- ((4-methoxyphenyl) thio) phenol comprising the following experimental steps:
under the condition of room temperature, sequentially adding 1b (1mmol) of o-bromodisulfide, 3mL of DMSO (dimethyl sulfoxide) solvent, 2b (0.45mmol) of p-methoxyiodobenzene and 1mmol of cesium carbonate into a reactor, stirring at room temperature to fully dissolve the o-bromodisulfide, adding an MOF-Cu catalyst (0.10% mol), reacting at 80 ℃ for 8 hours, firstly filtering out the MOF-Cu catalyst after TLC detection reaction is completed, then pouring the reaction system into 30mL of water, extracting with 15mL of dichloromethane for three times, drying with anhydrous sodium sulfate, removing dichloromethane under reduced pressure, and carrying out column chromatography on the residue to obtain the target compound 3b with the yield of 63%.
1H NMR(400MHz,CDCl3)δ(ppm)7.23(d,J＝7.2Hz,1H,Ar-H),7.20–7.13(m,3H,Ar-H),7.05(s,1H,OH),7.01(d,J＝8.4Hz,1H,Ar-H),6.81(d,J＝8.8Hz,2H,Ar-H),3.76(s,3H,OCH3)；
13C NMR(100MHz,CDCl3)δ(ppm)158.92,132.29,131.21,130.07,125.18,124.37,120.08,114.94,114.28,109.72,55.33；
Example 4
A process for the preparation of 2- ((4- (tert-butyl) phenyl) thio) -5-chlorophenol comprising the following experimental steps:
under the condition of room temperature, adding p-chloro-disulfide compound 1c (1mmol), 3mL of DMSO (dimethyl sulfoxide) solvent, p-tert-butyl iodobenzene 2c (0.45mmol) and cesium carbonate (1mmol) into a reactor in sequence, stirring at room temperature to fully dissolve the p-chloro-disulfide compound, adding an MOF-Cu catalyst (0.10% mol), reacting at 80 ℃ for 8 hours, detecting the reaction completion through TLC, firstly filtering out the MOF-Cu catalyst, pouring the reaction system into 30mL of water, extracting with 15mL of dichloromethane for three times, drying with anhydrous sodium sulfate, removing dichloromethane under reduced pressure, and carrying out column chromatography on the residue to obtain the target compound 3c with the yield of 65%.
1H NMR(400MHz,CDCl3)δ(ppm)7.45(d,J＝8.0Hz,1H,Ar-H),7.26(d,J＝2.0Hz,2H,Ar-H),7.08(d,J＝2.0Hz,1H,Ar-H),7.03(d,J＝8.8Hz,2H,Ar-H),6.93(dd,J＝8.4,2.4Hz,1H,Ar-H),6.59(s,1H,OH),1.27(s,9H,3CH3)；
13C NMR(101MHz,CDCl3)δ(ppm)157.70,149.90,137.51,137.38,132.42,131.58,129.21,127.13,126.41,121.58,115.90,115.75,34.45,31.20；
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (4)
1. The application of the nanorod-shaped two-dimensional copper-based metal organic framework material in catalyzing carbon-sulfur coupling reaction of diaryl disulfide is characterized in that the chemical molecular formula of the crystalline material is [ Cu (1H-1,2,4-triazole-1-acetic acid ]2]nN is the infinite alternative arrangement of the simplest molecular formula of the internal component of the material, and the chemical formula of the minimum unit structure of the crystalline material is C8H8CuN6O4The crystal of the crystalline material belongs to a monoclinic system, the space group is P21/n, and the unit cell parameters are as follows: a = 4.8194A, b = 11.5250A, c =9.9298Å ；α＝γ＝90°，β=100.893°。
2. Use according to claim 1, wherein the method for preparing a two-dimensional copper-based metal-organic framework material in the shape of a nanorod comprises the following steps:
dissolving an organic ligand 1H-1,2,4-triazole-1-acetic acid in a mixed solution of N, N-dimethylformamide, deionized water and ethanol, performing ultrasonic treatment to obtain a uniformly dispersed suspension, adding copper nitrate, and reacting at 50-100 ℃ for 10-30 hours to obtain the metal organic framework crystal material.
3. Use according to claim 2, wherein the organic ligand 1H-1,2,4-triazole-1-acetic acid and copper nitrate are present in a molar ratio of 0.5 to 1: 1.
4. Use according to claim 2, wherein the thermal reaction conditions are 85 ℃ and the reaction time is 24 h.
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