In Situ SERS Monitoring and Heterogeneous Catalysis Verification of Pd-Catalyzed Suzuki–Miyaura Reaction via Bifunctional “Black Raspberry-like” Plasmonic Nanoreactors

Constructing materials that possess both catalytic properties and surface plasmonic active structures presents an essential requirement in the field of in situ surface-enhanced Raman spectroscopy (SERS) monitoring. In this work, we developed a novel black raspberry-like bifunctional nanoreactor platform (HPRS@Au–Pd) with enhanced surface-enhanced Raman spectroscopy (SERS) activity (EF = 3.11 × 109) and excellent catalytic performance (e.g., |K| = 1.72 × 10–2 s–1 for 4-BTP). This platform enables sensitive and real-time monitoring of Suzuki reactions, providing an efficient and stable system for mechanistic investigations. By fitting a first-order kinetic model, we quantitatively analyzed the reaction kinetics of haloarenes on Pd NPs, revealing the direct involvement of surface-bound Pd NPs in the catalytic process. Furthermore, 4MPBA-blocking experiments using haloarenes devoid of functional groups demonstrated the absence of catalytic activity from dissolved Pd species, conclusively supporting the heterogeneous nature of the reaction. This work extends the applicability of the conclusion regarding heterogeneous catalysis to a broader range of substrates, offering valuable insights into the design and optimization of dual-functional nanoreactors. Beyond the Suzuki reactions, the versatility of this platform opens avenues for applications in other catalytic reactions, showcasing its potential in advanced catalytic studies and real-time monitoring.