Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles

Xiao, Qi, Sarina, Sarina, Bo, Arixin, Jia, Jianfeng, Liu, Hongwei, Arnold, Dennis P, Huang, Yiming, Wu, Haishun, & Zhu, Huai Yong (2014) Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles. ACS Catalysis, 4(6), pp. 1725-1734.

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Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald–Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.

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24 citations in Scopus
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31 citations in Web of Science®

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ID Code: 88518
Item Type: Journal Article
Refereed: Yes
Keywords: alloy nanoparticles, cross-coupling, photocatalysis, surface plasmon resonance, visible light
DOI: 10.1021/cs5000284
ISSN: 2155-5435
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 04 Nov 2015 03:57
Last Modified: 04 Nov 2015 03:57

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