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Accurate metal cluster-based composite catalyst as well as preparation method and application thereof

A technology of composite catalysts and metal clusters, applied in the field of organic chemistry, can solve problems such as limited applications, frequent occurrence of extreme weather, and exacerbated instability of the climate system

Inactive Publication Date: 2022-06-07
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Excessive emissions of carbon dioxide into the atmosphere exacerbate the instability of the climate system, leading to frequent occurrence of extreme weather in some regions
Currently Cu / ZnO / Al 2 o 3 Industrial catalysts represented by catalysts are high temperature and high pressure, and their organic products are mainly methanol, which limits the application of carbon dioxide hydrogenation

Method used

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  • Accurate metal cluster-based composite catalyst as well as preparation method and application thereof
  • Accurate metal cluster-based composite catalyst as well as preparation method and application thereof
  • Accurate metal cluster-based composite catalyst as well as preparation method and application thereof

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preparation example Construction

[0037] The technical scheme is that the number of atoms is 9, 25 and 44, and the metal type is gold, silver, palladium, platinum and metal nanoclusters of alloys of the above metals are composite catalysts with active centers, and the specific preparation method includes the following steps:

[0038] ①Ligand coordination and multi-distribution metal sol molding: prepare a solution of metal precursors or a mixed solution of metal precursors with a mass fraction of 1% to 10%. One or more of the above-mentioned metal salt solutions or suspension solutions are added to the flask, and under vigorous stirring, organic phosphine ligands or thiol ligands with a mass of 0.5 to 10 times the molar weight of the metal salt are added to the liquid phase. middle;

[0039] ②NaBH 4 Reduction: prepare sodium borohydride (NaBH) with a mass fraction of 0.1% to 5% 4 )The solution. The above NaBH 4 The solution (0.1-10 ml) is added dropwise or rapidly to the solution in step ①, and after conti...

Embodiment 1

[0046] Dissolve 1600 mg of tetrachloroauric acid in 40 ml of dichloromethane, stir to obtain a yellow transparent solution, add 2350 mg of triphenylphosphine and continue stirring for 30 minutes to obtain a colorless solution. Then, 500 mg of tetrakistriphenylphosphine palladium was dissolved in 40 ml of dichloromethane, and a dark red transparent solution was obtained after stirring. The above two solutions were added to a 200-mL flask, and after stirring for 10 minutes, a dark purple solution was obtained. 76 mg NaBH 4 Dissolve in 20 mL of ethanol solution and add this solution dropwise to the flask. After 30 minutes of reaction, the product was evaporated to dryness using a rotary evaporator to obtain a black solid. The solid was extracted with 40 mL of ethanol and filtered through celite, and the filtrate was evaporated to dryness in vacuo. The resulting black solid was washed three times with ether, extracted with dichloromethane and dried by vacuum evaporation to give...

Embodiment 2

[0050] Dissolve 1600 mg of tetrachloroauric acid in 80 ml of dichloromethane, stir to obtain a yellow transparent solution, add 2350 mg of triphenylphosphine, and continue stirring for 30 minutes to obtain a colorless solution. Then, silver nitrate was added in a 1.5-fold molar amount of tetrachloroauric acid. After stirring for 60 minutes, a colorless solution was obtained, which was transferred to a 200 mL flask. 76 mg NaBH 4 Dissolve in 20 mL of ethanol solution and add this solution dropwise to the flask. After 30 minutes of reaction, the product was evaporated to dryness using a rotary evaporator to give a black solid. The solid was extracted with 40 mL of ethanol and filtered through celite, and the filtrate was evaporated to dryness in vacuo. The resulting black solid was washed three times with ether, extracted with dichloromethane and dried by vacuum evaporation to give a black solid. Through ultraviolet-visible spectroscopy (UV-Vis) test, the obtained metal nanoc...

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Abstract

The invention discloses a precise metal cluster-based composite catalyst as well as preparation and application thereof. According to the precise metal cluster-based composite catalyst, a metal nanocluster of metal gold, silver, palladium, platinum or alloys thereof is used as an active center and is compounded with a carrier with ion exchange capacity to form the catalyst. The catalyst disclosed by the invention has excellent catalytic performance when being applied to catalysis of carbon-carbon coupling reactions such as carbon dioxide reduction coupling and Suzuki cross coupling reactions. The material has a plurality of advantages and has a certain industrial application prospect. The catalyst in the method is low in metal content, high in efficiency, low in cost and small in environmental pollution.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and particularly relates to a precise metal cluster-based composite catalyst, a preparation method thereof, and its application in catalyzing carbon-carbon coupling reactions. Background technique [0002] Precision metal nanoclusters, also known as ultra-small metal nanoparticles, fill the gap between isolated atoms and plasmonic nanomaterials, and are an emerging class of atomically precise nanomaterials. As a bridge between homogeneous catalysis and heterogeneous catalysis, precision metal nanoclusters can be used as a new type of catalyst with precise structure. Precision metal nanoclusters have unique physical and chemical properties, such as their precise and richly tunable geometric structure and atomic composition, as well as molecular-like behavior and special electronic properties in electronic structure. In addition, through the synergistic effect of metal components and their periphe...

Claims

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Application Information

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IPC IPC(8): B01J23/52B01J31/08B01J37/16B82Y30/00B82Y40/00C07C1/12C07C9/04C07C9/06C07C1/32C07C15/14
CPCB01J23/52B01J31/08B01J37/16B82Y30/00B82Y40/00C07C1/12C07C1/321B01J2231/4205B01J2231/4211B01J35/40C07C9/04C07C9/06C07C15/14
Inventor 祝艳蔡潇丁维平
Owner NANJING UNIV
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