VSe_2–xO_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.

Exploring and Engineering 2D Transition Metal Dichalcogenides toward Ultimate SERS Performance

“…As shown in Figure 12d, Li et al proposed hybridized VSe 2−x O x @Pd sensors to track the molecular dynamics in Pdcatalyzed reactions. [128] Benefiting from metal−support interactions, the VSe 2−x O x @Pd realizes strong charge transfer and enriched DOS near the Fermi level, thereby intensifying the charge transfer process to the adsorbed molecules and consequently enhancing the Raman signals. They demonstrated the feasibility of SERS monitoring of Pd-catalyzed reactions by employing 2D TMDs SERS substrates, overcoming the drawback of plasmon-induced side effects of conventional noble metal SERS substrates.…”

“…Copyright 2020, American Chemical Society. d-f) Reproduced with permission [128]. Copyright 2023, The Authors.…”

Design of MXene-Based Multiporous Nanosheet Stacking Structures Integrating Multiple Synergistic SERS Enhancements for Ultrasensitive Detection of Chloramphenicol

“…Fundamentally, the pivotal research objective receiving the most attention regarding SERS technology is developing ultrasensitive and stable enhanced substrates for achieving trace SERS detection of CAP molecules. It is well acknowledged that electromagnetic enhancement (EM) and chemical enhancement (CM) are the most well-established enhancement mechanisms of Raman signals enhanced by SERS substrates. − Integration of the multiple contributions of CM and EM into nonmetallic SERS substrates may be a promising approach to significantly improve SERS sensitivity. As atomically thin semimetallic 2D materials, MXenes exhibit many fascinating properties such as conductivity, tunable electronic structure, high carrier mobility, high electronic density of states near the Fermi level, and the ability to achieve strong light–matter interaction at mid-infrared and THZ frequencies, − which is expected to endow MXenes with excellent SERS performance.…”

Ferroelectrically modulate the Fermi level of graphene oxide to enhance SERS response

“…Seo et al optimized the complementary resonance effects between the substrate and probe molecule by varying the oxygen concentration in the ReO x S y thin film 20 . Liang et al developed a two-dimensional (2D) borocarbonitride (BCN) SERS platform with adjustable CB level by changing the carbon atomic ratio for detection of specific molecular with appropriate band structure 21 . Zhou et al developed a molecular adsorption strategy to regulate the CT efficiency between rGO and target molecules by controlling the adsorption or desorption of gas molecules on rGO surface 23 .…”