Differentiating Plasmon-Enhanced Chemical Reactions on AgPd Hollow Nanoplates through Surface-Enhanced Raman Spectroscopy

作者：Sulin Jiao, Kun Dai, Lucas V. Besteiro, Hongen Gao, Xuan Chen, Weichao Wang, Yuan Zhang, Chuntai Liu, Ignacio Pérez‐Juste, Jorge Pérez‐Juste, Isabel Pastoriza‐Santos, Guangchao Zheng · 发表于：ACS Catalysis · 年份：2024 · DOI：10.1021/acscatal.3c06253 · 被引用次数：29 · 研究领域：Gold and Silver Nanoparticles Synthesis and Applications、Copper-based nanomaterials and applications、Nanocluster Synthesis and Applications

Plasmonic photocatalysis demonstrates great potential for efficiently harnessing light energy. However, the underlying mechanisms remain enigmatic due to the transient nature of the reaction processes. Typically, plasmonic photocatalysis relies on the excitation of surface plasmon resonance (SPR) in plasmonic materials, such as metal nanoparticles, leading to the generation of high-energy or "hot electrons", albeit accompanied by photothermal heating or Joule effect. The ability of hot electrons to participate in chemical reactions is one of the key mechanisms, underlying the enhanced photocatalytic activity observed in plasmonic photocatalysis. Interestingly, surface-enhanced Raman scattering (SERS) spectroscopy allows the analysis of chemical reactions driven by hot electrons, as both SERS and hot electrons stem from the decay of SPR and occur at the hot spots. Herein, we propose a highly efficient SERS substrate based on cellulose paper loaded with either Ag nanoplates (Ag NPs) or AgPd hollow nanoplates (AgPd HNPs) for the in situ monitoring of C-C homocoupling reactions. The data analysis allowed us to disentangle the impact of hot electrons and the Joule effect on plasmon-enhanced photocatalysis. Computational simulations revealed an increase in the rate of excitation of hot carriers from single/isolated AgPd HNPs to an in-plane with a vertical stacking assembly, suggesting its promise as a photocatalyst under broadband light. In addition, the results suggest that the in...