Unraveling Surface Plasmon Decay in Core–Shell Nanostructures toward Broadband Light-Driven Catalytic Organic Synthesis

Abstract

Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.

Exploration of Zr–Metal–Organic Framework as Efficient Photocatalyst for Hydrogen Production

“…1b) clearly shows that the lattice spacing of the quantum-sized Pd nanoparticles is ca. 0.223 nm, which is consistent with the lattice spacing of the (111) plane of metallic Pd [48]. It can be clearly seen that the Pd nanoparticles were uniformly distributed on the surface of UiO-66 ( Fig.…”

“…In 2015, Yuan and coworkers described a very simple system using erythrosine B dye to sensitize UiO-66 and the highest H 2 production rate of 4.6 μmol h −1 [47]. In 2016, Xiao and coworkers described a Pt@UI-66-NH 2 catalytic system with a very high hydrogen production activity (257.38 μmol g −1 h −1 ) [48]. The synergistic of metal-organic frameworks and metal nanoparticles for enhanced catalysis is systematically reviewed in Jiang' work [49,50].…”

Hot‐Electron‐Mediated Photochemical Reactions: Principles, Recent Advances, and Challenges

“…Recently, Huang et al experimentally proved that hot electrons sometimes affect plasmon-induced organic synthesis negatively. [39] Based on atomiclevel control of the Pd shell thickness on Au nanorods (AuNRs), the authors successfully clarified the role of these two effects in catalytic performance, and maximized the catalytic efficiency via delicate material design. This new understanding provides material design guidelines for other types of reactions, where the plasmonic hot electrons can achieve positive contributions.…”

Photothermal-enhanced catalysis in core–shell plasmonic hierarchical Cu7S4microsphere@zeolitic imidazole framework-8

“…6–10 Comparing the two mechanisms, the heating pathway is supposed to be a versatile strategy due to lower requirements of the surface properties of the catalyst. According to collision theory, the proportion of reactant molecules with energy larger than the activation energy ( E > E a ) increases after absorbing heat, bringing about more successful collisions and a corresponding increase in reaction rate.…”