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石墨烯负载铜纳米粒子:可见光下促进硝基芳烃偶联反应的高效光催化剂。

Copper nanoparticles on graphene support: an efficient photocatalyst for coupling of nitroaromatics in visible light.

机构信息

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Taiyuan 030001 (China).

出版信息

Angew Chem Int Ed Engl. 2014 Feb 10;53(7):1973-7. doi: 10.1002/anie.201309482. Epub 2014 Jan 21.

Abstract

Copper is a low-cost plasmonic metal. Efficient photocatalysts of copper nanoparticles on graphene support are successfully developed for controllably catalyzing the coupling reactions of aromatic nitro compounds to the corresponding azoxy or azo compounds under visible-light irradiation. The coupling of nitrobenzene produces azoxybenzene with a yield of 90 % at 60 °C, but azobenzene with a yield of 96 % at 90 °C. When irradiated with natural sunlight (mean light intensity of 0.044 W cm(-2) ) at about 35 °C, 70 % of the nitrobenzene is converted and 57 % of the product is azobenzene. The electrons of the copper nanoparticles gain the energy of the incident light through a localized surface plasmon resonance effect and photoexcitation of the bound electrons. The excited energetic electrons at the surface of the copper nanoparticles facilitate the cleavage of the NO bonds in the aromatic nitro compounds. Hence, the catalyzed coupling reaction can proceed under light irradiation and moderate conditions. This study provides a green photocatalytic route for the production of azo compounds and highlights a potential application for graphene.

摘要

铜是一种低成本的等离子体金属。在可见光照射下,成功地开发了在石墨烯载体上的铜纳米粒子作为高效光催化剂,可控催化芳香族硝基化合物与相应的偶氮或重氮化合物的偶联反应。在 60°C 时,硝基苯的偶联反应生成了 90%的偶氮苯,但在 90°C 时生成了 96%的偶氮苯。当用自然阳光(平均光强为 0.044 W cm(-2) )在 35°C 左右照射时,70%的硝基苯被转化,57%的产物是偶氮苯。铜纳米粒子中的电子通过局域表面等离子体共振效应和束缚电子的光激发获得入射光的能量。铜纳米粒子表面的激发能电子促进了芳香族硝基化合物中 NO 键的断裂。因此,在光照射和温和条件下可以进行催化偶联反应。本研究为偶氮化合物的生产提供了一种绿色的光催化途径,并突出了石墨烯的潜在应用。

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