VSe _{2– x} O _x @Pd Sensor for Operando Self-Monitoring of Palladium-Catalyzed Reactions

Abstract

Operando monitoring of catalytic reaction kinetics plays a key role in investigating the reaction pathways and revealing the reaction mechanisms. Surface-enhanced Raman scattering (SERS) has been demonstrated as an innovative tool in tracking molecular dynamics in heterogeneous reactions. However, the SERS performance of most catalytic metals is inadequate. In this work, we propose hybridized VSe _{2– x} O _x @Pd sensors to track the molecular dynamics in Pd-catalyzed reactions. Benefiting from metal–support interactions (MSI), the VSe _{2– x} O _x @Pd realizes strong charge transfer and enriched density of states near the Fermi level, thereby strongly intensifying the photoinduced charge transfer (PICT) to the adsorbed molecules and consequently enhancing the SERS signals. The excellent SERS performance of the VSe _{2– x} O _x @Pd offers the possibility for self-monitoring the Pd-catalyzed reaction. Taking the Suzuki–Miyaura coupling reaction as an example, operando investigations of Pd-catalyzed reactions were demonstrated on the VSe _{2– x} O _x @Pd, and the contributions from PICT resonance were illustrated by wavelength-dependent studies. Our work demonstrates the feasibility of improved SERS performance of catalytic metals by modulating the MSI and offers a valid means to investigate the mechanisms of Pd-catalyzed reactions based on VSe _{2– x} O _x @Pd sensors.