Preparation method of MOFs with pi-activation catalytic action

A catalyst and ligand technology, applied in the field of heterogeneous catalytic materials, can solve the problems of low utilization rate of noble metal silver atoms, impossibility of alkyne π-activation, difficult separation and purification, etc., to achieve easy large-scale application and improve activity And catalytic conversion number, low price effect

Active Publication Date: 2017-01-04
DALIAN UNIV OF TECH
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Problems solved by technology

[0005] Traditional metal-organic frameworks are generally only capable of acid-base catalysis, and cannot perform π-activation on the carbon-carbon triple bond of alkynes
However, in the existing homogeneous noble metal silver catalysts with π-activation, the utilization rate of noble metal silver atoms is not high, and it is not easy to recycle, and there are heavy metal residues in the product, which is difficult to separate and purify

Method used

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  • Preparation method of MOFs with pi-activation catalytic action
  • Preparation method of MOFs with pi-activation catalytic action
  • Preparation method of MOFs with pi-activation catalytic action

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Experimental program
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Effect test

Embodiment 1

[0038] Mix 2,4,6-tris(4-acetyl-phenylamino)-1,3,5-triazine (4.81g, 10mmol) and thiosemicarbazide (2.27g, 25mmol) into 40mL of ethanol, reflux at 80°C for 10h , filtered with suction, rinsed with methanol, and dried in vacuo to obtain light yellow solid ligand TzNPAMeTs. Yield: 3.5 g, 50%. 1H-NMR[400MHz,DMSO-d6,ppm]:10.15(s,1H,-NH),9.65(s,1H,Ar-NH-),8.25(s,1H,-NH2),7.98-7.77(m ,5H,Ar-H and-NH2).13C-NMR[500MHz,DMSO-d6,ppm]: 178.59,171.97,147.85,140.72,131.27,126.95,119.60,13.78.ESI-MS:m / z 700.20.

[0039] In a thin glass test tube, the ligand TzNPAMeTs (0.01mmol, 7.0mg) was added to 1mL N,N-dimethylformamide solution to make the lower layer solution, and then the metal silver salt AgBF 4 (0.03mmol, 5.8mg) was added to 1mL of acetonitrile to make the upper layer solution, the middle layer was 1mL of a mixed solution of N,N-dimethylformamide and acetonitrile with a volume ratio of 1:5. , after about 4 weeks, colorless to pale yellow crystals precipitated, which was the catalyst...

Embodiment 2

[0041] Mix thiosemicarbazide (2.73g, 30mmol) and 2,4,6-tris(4-acetyl-phenylamino)-1,3,5-triazine (4.81g, 10mmol) into 50mL of ethanol, reflux at 85°C for 12h , filtered with suction, rinsed with methanol, and dried in vacuo to obtain light yellow solid ligand TzNPAMeTs. Yield: 6.3 g, 90%. 1H-NMR[400MHz,DMSO-d6,ppm]:10.15(s,1H,-NH),9.65(s,1H,Ar-NH-),8.25(s,1H,-NH2),7.98-7.77(m ,5H,Ar-H and-NH2).13C-NMR[500MHz,DMSO-d6,ppm]: 178.59,171.97,147.85,140.72,131.27,126.95,119.60,13.78.ESI-MS:m / z 700.20.

[0042] In a thin glass test tube, the ligand TzNPAMeTs (0.01mmol, 7.0mg) was added to 1mL N,N-dimethylformamide solution to make the lower layer solution, and then the metal silver salt AgBF 4 (0.03mmol, 5.8mg) was added to 1mL of acetonitrile to make the upper layer solution, the middle layer was 1mL of a mixed solution of N,N-dimethylformamide and acetonitrile with a volume ratio of 5:1. , after about 4 weeks, colorless to pale yellow crystals precipitated, which was the catalyst...

Embodiment 3

[0044] Mix thiosemicarbazide (3.18g, 35mmol) and 2,4,6-tris(4-acetyl-phenylamino)-1,3,5-triazine (4.81g, 10mmol) into 60mL of ethanol, reflux at 90°C for 15h , filtered with suction, rinsed with methanol, and dried in vacuo to obtain light yellow solid ligand TzNPAMeTs. Yield: 6.7 g, 95%. 1H-NMR[400MHz,DMSO-d6,ppm]:10.15(s,1H,-NH),9.65(s,1H,Ar-NH-),8.25(s,1H,-NH2),7.98-7.77(m ,5H,Ar-H and-NH2).13C-NMR[500MHz,DMSO-d6,ppm]: 178.59,171.97,147.85,140.72,131.27,126.95,119.60,13.78.ESI-MS:m / z700.20.

[0045] In a thin glass test tube, the ligand TzNPAMeTs (0.01mmol, 7.0mg) was added to 1mL N,N-dimethylformamide solution to make the lower layer solution, and then the metal silver salt AgBF 4 (0.03mmol, 5.8mg) was added to 1mL of acetonitrile to make the upper layer solution, the middle layer was 1mL of a mixed solution of N,N-dimethylformamide and acetonitrile with a volume ratio of 1:1. , after about 4 weeks, colorless to pale yellow crystals precipitated, which was the catalyst ...

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Abstract

The invention relates to the technical field of heterogeneous catalytic materials, in particular to a preparation method of MOFs with a pi-activation catalytic action. The preparation method is characterized in that L1 and L2 are used as ligands; the ligands and metallic silver salt Tm are prepared by a stratified dispersal method to obtain a catalyst Ag8-MOF or Ag4-MOF with a plane coordination configuration, metal cluster nodes and the pi-activation catalytic action. A synthetic route of the catalyst is as follows: Tm+L1-Ag8-MOF or Tm+L2-Ag4-MOF; the ligand L1 is selected from TzNPAMeTs, and the L2 is selected from TzOPATs; the metallic silver salt Tm is selected from AgCF3COO or AgBF4. According to the preparation method disclosed by the invention, the synthesis of the catalyst is simple and easy to operate; catalytic reaction raw materials are low in price and high in yield, and are easy for large-area popularization and application. By regulating and controlling immobilization and coordination configuration of precious metal through thioamide ligands, the activity of the catalyst and catalytic conversion number are greatly improved; the easiness for recycling is realized, and the utilization rate of the precious metal is greatly improved, thereby reducing the integration cost of the whole catalytic cycle; the preparation method is suitable for meeting industrial large-scale production.

Description

technical field [0001] The invention relates to a method for preparing MOFs with π-activated catalysis, and belongs to the technical field of heterogeneous catalytic materials. Background technique [0002] Oxazolidinone antibiotics are a new type of fully synthetic antibiotics developed gradually in the 1980s. This type of drug has an oxazolidinone core in its chemical structure and has a new antibacterial mechanism. It has strong antibacterial activity against Gram-positive cocci, especially multi-drug-resistant Gram-positive cocci. It is different from other drugs. Cross-resistance exists. From an environmental and economic point of view, CO 2 It is cheap, non-toxic and non-flammable, and can be used as a ready-made C1 building block to react with epoxy compounds without generating by-products. [0003] In recent years, some research groups at home and abroad are developing new catalytic systems to catalyze the utilization of CO 2 Research work has been carried out, s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D251/70C07D251/34C07F1/10B01J31/22C07D263/38
CPCB01J31/22B01J2531/0238B01J2531/17C07D251/34C07D251/70C07D263/38C07F1/10
Inventor 段春迎常智舵何成
Owner DALIAN UNIV OF TECH
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