Interface-Controlled Pd Nanodot-Au Nanoparticle Colloids for Efficient Visible-Light-Induced Photocatalytic Suzuki-Miyaura Coupling Reaction

Abstract

Plasmonic nanostructures can be employed for performing photocatalytic reactions with visible-light illumination involving two different possible mechanisms, namely, the near-field enhancement and/or direct hot-electron transfer to the conduction band of an active catalyst. In this study, we demonstrate the significant contribution of a graphene interface layer present between plasmonic nanoparticles and active catalysts (Pd nanodots) in enhancing the photocatalytic efficiency of Pd nanodots through an accelerated electron transfer process. The well-defined Pd-nanodot-modified gold nanoparticles with or without a graphene interface layer were prepared using a wet-chemical synthetic method. The role of the graphene interface was investigated by performing wavelength-dependent reduction studies using potassium hexacyanoferrate (III) in the presence of Pd-nanodot-modified cysteamine-modified AuNPs (Pd-cys-AuNPs), Pd-nanodot-modified graphene oxide (GO)-coated AuNPs (Pd-GO-AuNPs), and Pd-nanodot-modified reduced GO (rGO)-coated AuNPs (Pd-rGO-AuNPs). The fastest rate for the reduction of Fe3+ to Fe2+ was obtained with Pd-rGO-AuNPs because of the fast electron transfer achieved in the presence of the reduced graphene oxide layer. The highest catalytic activity for the visible-light induced C-C coupling reaction was obtained with Pd-rGO-AuNPs, indicating the role of the graphene interface layer. These results indicate that the design and use of engineered interfaces are of importance to achieve enhanced catalytic activity with plasmonic hybrid nanomaterials.

Plasmonic heating using an easily recyclable Pd‐functionalized Fe3O4/Au core‐shell nanoparticle catalyst for the Suzuki and Sonogashira reaction

“…For chemical reactions, the plasmonic heating has been utilized using Au or Ag nanocrystals to drive the oxidation of formaldehyde and methanol, 45 the reduction of nitroaromatic compounds, 46 the acceleration of CO oxidation 47 and the ethylene epoxidation 48 . Furthermore, Au nanoparticles or nanorods have been used for photocatalytic Suzuki cross‐coupling reactions 35–37 . These results demonstrate clearly the possibility of using plasmonic metal nanocrystals and nanoparticles as energy converters and catalysts to drive chemical reactions at moderate temperatures.…”

“…A lot of efforts have been made to synthesize recoverable catalysts, such as Pd nanoparticles 5–7 and Pd immobilized on silica nanoparticles, 8–11 graphene, 12–14 polymers, 15–20 carbon nanotubes, 21, 22 and dendrimers 23–26 . Furthermore, Pd has also been immobilized on metal–organic frameworks, 27 metal oxides, 28–30 metal oxide nanoparticles 31–34 and gold nanoparticles for the use in plasmon‐assisted cross‐coupling reactions, resulting in localized heating 35–37 . Another type of local heating was recently examined using magnetic induction, resulting in an easily magnetically recyclable nanoparticle, which increases the control and safety of the reaction 38 .…”

Structure controlled Au@Pd NPs/rGO as robust heterogeneous catalyst for Suzuki coupling in biowaste‐derived water extract of pomegranate ash

“…[ 28 ] Additionally, Au–Pd NPs are well studied for their acceleration ability of reaction rates in Suzuki coupling with an effective recapture of Pd in the presence of an electronegative Au. In this connection, hyper‐cross‐linked polystyrene supported Au@Pd NPs, [ 19 ] Au@Pd NPs, [ 18,29,30 ] biodeposited Au–Pd NPs, [ 31 ] ferrite–dopamine supported Au–Pd NPs, [ 32 ] Au‐Pd NPs supported on SiO 2 or MCM–41, [ 33 ] SBA–15 stabilized Au–Pd alloy NPs, [ 34 ] Au–Pd alloy NPs, [ 35 ] Au–Pd NPs dispersed on TiO 2, [ 36 ] Au–Pd alloy NPs supported on ZrO 2, [ 37 ] and Pd nanodot–Au NP colloids [ 38 ] were described for Suzuki cross‐coupling at various conditions including microwave or photoirradiations. [ 34–38 ] Nevertheless, the necessity of additional base, [ 18,29–38 ] poor reusability, [ 18 ] poor yields with certain substrates, [ 31–36 ] organic solvents such as DMF [ 35,37 ] or THF, [ 32 ] and large reaction times [ 18,29–32,35 ] limits the wide spread usage of these processes.…”

Catalysts for Suzuki–Miyaura Coupling Reaction

“…The best productivity (95%) is obtained in the presence of Pd/GO-TiO 2 , which is also successfully recycled in four subsequent runs. After a few recyclings, the selectivity to ketones decreases and normal Suzuki-Miyaura coupling occurs.Pd-nanodot-modified gold nanoparticles with or without a graphene interface layer are prepared using a wet-chemical synthetic method [5]. Among the different catalysts, Pd-rGO-AuNPs permit the highest catalytic activity for the visible-light-induced C-C bond coupling reaction.…”

“…Pd-nanodot-modified gold nanoparticles with or without a graphene interface layer are prepared using a wet-chemical synthetic method [5]. Among the different catalysts, Pd-rGO-AuNPs permit the highest catalytic activity for the visible-light-induced C-C bond coupling reaction.…”