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

Abstract

Palladium functionalized gold nanoparticles were used in the past as a catalyst system in light induced cross‐coupling reactions, but with a main limitation of the recuperation. To overcome this problem, a palladium functionalized Fe3O4/Au core‐shell nanoparticle was successfully synthesized with a peak wavelength of 680 nm from the plasmon resonance of the gold shell. By the presence of the magnetite core, the nanoparticle catalyst can easily be removed using magnetic precipitation. This is accompanied with the advantage of having less valuable gold present in the system. The gold shell makes it possible to induce local heating using plasmon resonance. By this combination, it is possible to recuperate the catalyst system using magnetic precipitation and increase the control and safety of the reaction due to the presence of the light‐induced plasmonic heating. It was possible to perform light‐induced Suzuki cross‐coupling reactions using this catalyst system, but with a dependency of the substrate. It was found that an anionic substrate is repulsed from the negatively charged core‐shell nanoparticle. The catalyst was examined on its recuperation abilities and could be reused up to 5 cycles. At the catalytic site a temperature was reached between 40 °C and 45 °C. Despite the promising results of the Suzuki reaction, it was not possible to perform light‐induced Sonogashira reactions due to the insufficient heat generation at the catalytic site. Nevertheless, these results are promising in the development of an easily recyclable catalyst together with an alternative heating source, resulting in an increase of control and safety.

Photoinduced CO2 Conversion under Arctic Conditions─The High Potential of Plasmon Chemistry under Low Temperature

“…In general, CO 2 is a relatively inert molecule and its activation suffers from energy efficiency and poor reaction rates. − Thus, photocatalytic CO 2 activation using sunlight is very attractive due to the availability and zero cost of this energy source even in the North territories. − From photocatalysis studies performed at common temperatures, we learned different strategies for CO 2 activation, including the exploration of novel semiconductors with narrow band gaps and the development of specific catalytic surface sites. − The main idea here is to change the reaction pathways and decrease the “apparent” reaction activation barrier for CO 2 activation. This can be achieved photoelectrochemically through changes in the electronic or polarization states of the materials (both catalysts or reagents). , In the case of plasmon-assisted photochemistry, the light energy is used for plasmon excitation with a related appearance of hot charge carriers or high-energy states, which can be transferred to surrounding materials. , In most related works, the plasmon-assisted process accelerates the electrochemical reduction of CO 2 , with the formation of various products, such as CO, CH 3 OH, or CH 4 . − For the transformation of CO 2 into fine organic products, the lowering of the apparent reaction activation barrier to close to zero level has also been reported, using plasmon excitation on the surface of noble-metal nanostructures. − As a result, plasmon-assisted chemical transformations can be performed at significantly lower temperatures, compared to traditional reaction routes. − …”

Amine Functionalization Within Hierarchically‐Porous Zeotype Framework for Plasmonic Catalysis over PdAu Nanoparticles

“…[23] Koeckelberghs's group reported a 57 % product yield of 4-methylbipheyl utilizing Fe 3 O 4 /Au/PEG/Pd nanocatalyst. [24] A list of recently published Pd-based plasmonic catalytic systems has been tabulated (Table S1) to understand the current scenario in the efficiency of product formation. In this report, to further increase the catalytic performance of the Suzuki-Miyaura coupling reaction under solar light irradiation, we have experimented with the use of surface-functionalized zeotype materials with the addition of different kinds of amines, for example, primary (À RNH 2 ), secondary (À NHR 2 ), tertiary (À NR 3 ) groups and the presence of one, two and three nitrogen atoms containing amines.…”

“…have recently reported the design of Pd−Au NPs supported on ZrO 2 with a SiO 2 layer between Au and Pd NPs, displaying a biphenyl product yield=63.1 % [23] . Koeckelberghs's group reported a 57 % product yield of 4‐methylbipheyl utilizing Fe 3 O 4 /Au/PEG/Pd nanocatalyst [24] . A list of recently published Pd‐based plasmonic catalytic systems has been tabulated (Table S1) to understand the current scenario in the efficiency of product formation.…”

On‐Water and Efficient Ullmann‐Type O‐Arylation Cross Coupling Reaction of Phenols and Aryl Tosylates in the Presence of Fe3O4@Starch‐Au as Nanocatalyst

“…These days gold is considered as an extraordinary catalyst in many important reactions such as oxidation, epoxidation and C−C bond formation [10,11] . Supported gold nanoparticles use as an effective catalyst for cross coupling reactions, which become a common synthetic procedure for the synthesis of organic compounds with C sp2 −C sp2 linkage [12,13] …”