Visible to near-infrared plasmon-enhanced catalytic activity of Pd hexagonal nanoplates for the Suzuki coupling reaction

Abstract

Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111} and six {100} planes. The Pd hexagonal nanoplates with well-defined and tunable longitudinal localized surface plasmon resonance (LSPR) have enabled the direct harvesting of visible to near-infrared light for catalytic cross coupling reactions. Upon plasmon excitation, the catalytic Suzuki coupling reactions of iodobenzene and phenylboronic acid accelerate by a plasmonic photocatalytic effect of plasmon induced hot electrons. The turnover frequency (TOF) of the Pd hexagonal nanoplates in a reaction illuminated with a λ = 300-1000 nm Xenon lamp at 176 mW cm(-2) was 2.5 and 2.7 times higher than that of non-plasmonic {111}-enclosed Pd nanooctahedra and {100}-enclosed Pd nanocubes, respectively, and 1.7 times higher than the TOF obtained when the reaction was thermally heated to the same temperature.

Addressing the Effects of Size‐dependent Absorption, Scattering, and Near‐field Enhancements in Plasmonic Catalysis

“…Several studies on plasmonic catalysis and LSPR‐mediated catalytic transformations have focused on the demonstration of this phenomenon, quantification of reaction rates, and investigation of plasmonic enhancement mechanisms towards a variety of transformations (oxidation, couplings and reductions, for example) . For instance, it has been demonstrated that the main mechanisms by which LSPR excitation can accelerate or mediate these transformations may occur due to localized heating and charge transfer (direct and indirect pathways) as a result of LSPR excitation ,,.…”

Formation of strong L10-FePd/α-Fe nanocomposite magnets by visualizing efficient exchange coupling

“…1a): (1) synthesis of monodisperse Pd nanocubes (NCs) ( Fig. 1b and S1a-f †); 16,17 (2) homogeneous growth of FeO x shells on Pd NCs (Fig. 1c, S1g and Table S2 †); 18 (3) reduction-diffusion of Pd/FeO x core/shell (Pd@FeO x ) NCs under the ow of 4% H 2 gas (Ar balance) ( Fig.…”

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

“…It was reported that Pd nanoplates (twin crystals and their top and bottom faces are enclosed by {111} facets with stacking faults and side surfaces surrounded by a mixture of six {111} and six {100} facets) exhibited clear and well‐defined LSPR features . The LSPR peaks of Pd nanoplates were assigned to the longitudinal mode and could be tuned from 382 nm to 618 nm by changing the edge lengths from 31.7±10.5 nm to 60.4±19.3 nm while the thickness remains unchanged, which enabled direct harvesting of visible to near‐infrared light for catalytic Suzuki C−C cross‐coupling reactions.…”

“…Plasmonic Ag based bimetallic nanostructures were also employed in photocatalyzed cross-coupling reaction. In the work reported by Verma and coworkers, [16] the Pd/Ag bimetallic nanostructures with different size and morphology were [18] The LSPR peaks of Pd nanoplates were assigned to the longitudinal mode and could be tuned from 382 nm to 618 nm by changing the edge lengths from 31.7 � 10.5 nm to 60.4 � 19.3 nm while the thickness remains unchanged, which enabled direct harvesting of visible to near-infrared light for catalytic Suzuki CÀ C cross-coupling reactions. Upon plasmon excitation, the catalytic Suzuki CÀ C coupling reactions were accelerated by plasmon induced hot electrons.…”