Visible-Light-Activated Suzuki–Miyaura Coupling Reactions of Aryl Chlorides over the Multifunctional Pd/Au/Porous Nanorods of CeO₂ Catalysts

Abstract

Activation of aryl chlorides for Suzuki−Miyaura coupling (SMC) reactions is particularly challenging for heterogeneous catalysts due to the chemically inert nature of the C−Cl bond. Herein, the multifunctional Pd/Au/ porous nanorods of CeO 2 (PN-CeO 2 ) catalysts with a well-defined spatial configuration deliver the first example of heterogeneous catalysts to activate the strong C−Cl bond under the irradiation of visible light (>400 nm) at room temperature. PN-CeO 2 with strong basicity not only provides the photogenerated electrons to enrich the electron density of metal nanoparticles but also generates holes for activation of arylboronic acids. Meanwhile, due to the strong local surface plasma resonance, the hot electrons from Au nanoparticles excited by visible light can be injected into Pd nanocatalysts that are spatially contacted with Au nanoparticles. Thus, Pd nanocatalysts with significantly enriched electron density efficiently activate the aryl chlorides under the visible light irradiation at room temperature. The high catalytic activity and reusability of multifunctional photocatalysts associated with full use of the photogenerated electrons and holes inspire the future exploitation for the activation of unreactive chemical bonds under mild conditions.

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO2

“…PN -CeO 2 has been previously reported with a high surface Ce 3+ fraction (30.8%) and a large concentration of oxygen vacancy53545556. Besides, the surface properties of PN -CeO 2 can be effectively regulated by post-treatment with well preserved structural features, providing a platform to investigate the correlation between the hydrogenation activity of ceria and their surface properties.…”

Improving the rates of Pd-catalyzed reactions by exciting the surface plasmons of AuPd bimetallic nanotriangles

“…and spherical nanoparticles 16,20,26,37 have been used to improve the catalytic activity of palladium. Here, we employed plasmonic Au nanotriangles to harvest light in order to photophysically improve the rates of Pd-catalyzed reactions.…”

Heterogeneous Photocatalyzed C−C Cross‐coupling Reactions Under Visible‐light and Near‐infrared Light Irradiation

“…The final C−C bond can be formed by attacking radical anion of aryl halide through the aryl radical and followed by releasing the halogen anion. When using plasmonic photocatalysts (such as AuPd, Ag/Pd or supported nanostructures),,,,,,, the LSPR of metal (such as Au and Ag) enables light harvesting and promotes efficient conversion of light energy to hot electrons generation. The photoexcited electrons are then transferred to the reactant molecules that are adsorbed on the surface of photocatalyst to weaken the C−X bond and facilitate the reactions.…”