Plasmonic Catalysis: New Opportunity for Selective Chemical Bond Evolution

Abstract

Plasmonic catalysis is an ever-growing field in which chemical reactions are enabled by visible light excitation. The plasmonic effects provide a unique reaction environment, which can greatly affect chemical reaction processes. On the basis of extensive research on plasmon-induced chemical reactions, we focus on the fundamentals of plasmon-mediated catalytic selectivity and summarize recent advances and emerging opportunities in selective chemical bond evolution in this perspective. Taking representative reactions as examples, the unique feature and advantage of surface plasmons in modulating reaction selectivity are deciphered from the perspective of the three elementary steps: adsorption of reactants, activation of adsorbates, and desorption of products. In addition, nanoconfined plasmon-induced spatially selective reactions are also included. This perspective informs insights and opportunities for rationally engineering plasmonic catalytic systems toward purposeful solar energy utilization.

Hot-Electron-Driven Interfacial Chemistry Using Non-Noble Plasmonic Cu under Visible-Light Irradiation

“…1,2 To improve the light-to-energy conversion efficiency in visible-light photocatalysis, extensive efforts are applied to design and develop new heterogeneous photocatalysts. 3−5 Plasmonic metal nanoparticles (NPs) as emerging heterogeneous photocatalysts have aroused considerable interest 6,7 because of their large absorption cross sections in the visible region. As their most prominent feature, the metallic NPs have strong interactions with visible light to generate coherent oscillations of free electrons within the NPs, which is called localized surface plasmon resonance (LSPR).…”

“…Visible-light-driven photocatalysis has been a very promising strategy for solar-to-chemical energy conversion. , To improve the light-to-energy conversion efficiency in visible-light photocatalysis, extensive efforts are applied to design and develop new heterogeneous photocatalysts. − Plasmonic metal nanoparticles (NPs) as emerging heterogeneous photocatalysts have aroused considerable interest , because of their large absorption cross sections in the visible region. As their most prominent feature, the metallic NPs have strong interactions with visible light to generate coherent oscillations of free electrons within the NPs, which is called localized surface plasmon resonance (LSPR). , Via a nonradiative decay channel, excited surface plasmons in the metallic NPs would decay into energetic hot carriers (electron–hole pairs), where the high energy electrons are above the Fermi Level, while the hot holes are below it.…”

Photo-enhanced dehydrogenation of formic acid on Pd-based hybrid plasmonic nanostructures

“…In plasmonic catalysis, a hot charge carrier is widely regarded as one of the main mechanisms in promoting bond activation. 20,86,87 For a simple hybrid system composed of a plasmonic metal and an adsorbed molecule, there are two recognized charge transfer pathways, indirect and direct charge transfer. 20,22,88,89 In an indirect path, hot carriers are generated within the metal through Landau damping, and then injected into neighbouring chemisorbed molecules before fundamentally thermalizing into a low-energy carrier or recombination.…”

“…As a powerful tool, DFT calculation can well investigate the influence of electromagnetic fields on reaction thermodynamics, intermediates, hybrid electronic states, and so on. 86,104–106 The hybridized orbitals at the interface are redistributed under the action of electromagnetic fields, which may contribute to the direct dissipation of plasmon energy in these metal-molecular states. Such momentum conservation excitation avoids the metallic electron–electron and electron–phonon relaxation, resulting in some selective activation scenarios, and some unexpected phenomena.…”

Glutathione-Mediated Synthesis of Yolk–Shell AuAg Nanostructures Containing a Spherical Core and Cuboctahedral Skeletons and Their Applications in Plasmonic Catalysis

“…In addition, if the constituent element is plasmon-active, such an architecture also allows for multiple reflections of the electromagnetic waves within the hollow interiors and, thus, the efficient utilization of the incident light energy. To this end, the skeleton/frame-like noble metal nanostructure could be considered as an ideal candidate for plasmonic catalysis, 7 if the potential synergetic effects brought about by both the advantages that lie on catalysis and plasmonic absorptions are taken into consideration. 8 To create skeleton/frame-like noble metal nanostructures with a well-defined structure, typical wet-chemical syntheses are based on the "top-down" approaches.…”