Probing Oxidation Mechanisms in Plasmonic Catalysis: Unraveling the Role of Reactive Oxygen Species.

Plasmon-induced oxidation has conventionally been attributed to the transfer of plasmonic hot holes. However, this theoretical framework encounters challenges in elucidating the latest experimental findings, such as enhanced catalytic efficiency under uncoupled irradiation conditions and superior oxidizability of silver nanoparticles. Herein, we employ liquid surface-enhanced Raman spectroscopy (SERS) as a real-time and in situ tool to explore the oxidation mechanisms in plasmonic catalysis, taking the decarboxylation of p-mercaptobenzoic acid (PMBA) as a case study. Our findings suggest that the plasmon-induced oxidation is driven by reactive oxygen species (ROS) rather than hot holes, holding true for both the Au and Ag nanoparticles. Subsequent investigations suggest that plasmon-induced ROS may arise from hot carriers or energy transfer mechanisms, exhibiting selectivity under different experimental conditions. The observations were substantiated by investigating the cleavage of the carbon-boron bonds. Furthermore, the underlying mechanisms were clarified by energy level theories, advancing our understanding of plasmonic catalysis.

VSe2-x O x @Pd Sensor for Operando Self-Monitoring of Palladium-Catalyzed Reactions.

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 VSe2-x O x @Pd sensors to track the molecular dynamics in Pd-catalyzed reactions. Benefiting from metal-support interactions (MSI), the VSe2-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 VSe2-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 VSe2-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 VSe2-x O x @Pd sensors.

Flexible plasmonic nanocavities: a universal platform for the identification of molecular orientations.

The molecular orientation provides fundamental images to understand molecular behaviors in chemistry. Herein, we propose and demonstrate sandwich plasmonic nanocavities as a surface-selection ruler to illustrate the molecular orientations by surface-enhanced Raman spectroscopy (SERS). The field vector in the plasmonic nanocavity presents a transverse spinning feature under specific excitations, allowing the facile modulation of the field polarizations to selectively amplify the Raman modes of the target molecules. It does not require the knowledge of the Raman spectrum of a bare molecule as a standard and thus can be extended as a universal ruler for the identification of molecular orientations. We investigated the most widely used Raman probe, Rhodamine 6G (R6G) on the Au surface and tried to clarify the arguments about its orientations from our perspectives. The experimental results suggest concentration-dependent adsorption configurations of R6G: it adsorbs on Au primarily via an ethylamine group with the xanthene ring lying flatly on the metal surface at low concentrations, and the molecular orientation gradually changes from "flat" to "upright" with the increase of molecular concentrations.

Investigation of the Plasmon-Activated C-C Coupling Reactions by Liquid-State SERS Measurement.

The implementation of plasmonic materials in heterogeneous catalysis was limited due to the lack of experimental access in managing the plasmonic hot carriers. Herein, we propose a liquid-state surface-enhanced Raman scattering (SERS) technique to manipulate and visualize heterogeneous photocatalysis with transparent plasmonic chips. The liquid-state measurement conquers the difficulties that arise from the plasmon-induced thermal effects, and thus the plasmon based strategies can be extended to investigate a wider range of catalytic reactions. We demonstrated the selection of reaction products by modulating the plasmonic hot carriers and explored the mechanisms in several typical C-C coupling reactions with 4-bromothiophenol (4-BTP) as reactants. The real-time experimental results suggest brand new mechanisms of the formation of C-C bonds on plasmonic metal nanoparticles (NPs): the residue of 4-BTP, but not thiophenol (TP), is responsible for the C-C coupling. Furthermore, this technique was extended to study the evolution of the Suzuki-Miyaura reaction on nonplasmonic palladium metals by establishing the charge transfer channels between palladium and Au NPs. The cleavage and formation of chemical bonds in each individual reaction step were discerned, and the corresponding working mechanisms were clarified.

Origin of layer-dependent SERS tunability in 2D transition metal dichalcogenides.

Two-dimensional (2D) semiconductors are expected to replace noble metals to become the matrix materials of the next generation of commercial surface-enhanced Raman scattering (SERS) chips. Herein, we systematically studied the influence of the interlayer interaction on the SERS activity of 2D semiconductors from a brand-new perspective and comprehensively analyzed the physicochemical process of 2D semiconductor interlayer modulated SERS. Taking transition metal dichalcogenides as examples, we chose PtSe2 with strong interlayer interactions and ReS2 with weak interlayer interactions to analyze the physicochemical process of 2D semiconductor interlayer modulated SERS by first-principles calculations. PtSe2 and ReS2 samples with various thicknesses were prepared respectively, and the results of comparative experiments proved that the layer-dependent SERS tunability of 2D semiconductors is directly related to the interlayer interaction. This work provided a novel method for further improving the SERS detection limit of 2D semiconductors and a possible strategy for the industrial upgrading of commercial SERS chips.

Surface-Enhanced Raman Scattering Monitoring of Oxidation States in Defect-Engineered Two-Dimensional Transition Metal Dichalcogenides.

Recent studies have found that some transition metal dichalcogenides (TMDs) with their own defects are difficult to store in the air for a long time. Worse stability of TMDs under extreme conditions has also been reported. Therefore, monitoring the oxidation and degradation processes of TMDs can directly guide the stability prediction of TMD-based devices and monitor TMDs quality. Herein, with the case of molybdenum disulfide, UV-ozone defect engineering is used to simulate the oxidation and degradation of TMDs under severe conditions. Surface-enhanced Raman scattering based on a chemical mechanism was first introduced to the dynamic monitoring of defect evolution in the oxidation and degradation of TMDs, and succeeds in tracking the TMDs oxidation state by the quantitative method. It is expected that this technology can be extended to the quantification and tracking of oxidation and degradation of other 2D materials.

In situ detection of trace pollutants: a cost-effective SERS substrate of blackberry-like silver/graphene oxide nanoparticle cluster based on quick self-assembly technology.

To realize fast detection of trace hazardous chemicals, a SERS substrate with the structure of a blackberry-like silver/graphene oxide nanoparticle cluster (Ag/GO NPC) has been designed and prepared through a quick capillarity-assistant self-assembly technology in this paper. Benefitting from the abundant "hot spots" and active oxygen sites brought by this Ag/GO NPC, the substrate shows good Raman performance for malachite green (MG), a common abusive germicide in aquaculture, with lowest limit of detection below 0.1 µg/L (3.48 × 10-10 mol/L). Detailed analyses are taken on both the formation process and enhancement mechanism of this SERS substrate, and the finite-difference time-domain simulations are utilized as well to prove our hypotheses. Further constructing this structure on polyethylene terephthalate (PET) film, a translucent flexible SERS substrate can be obtained, realizing a fast in situ detection of trace MG in the fishpond subsequently. In consideration of the facile preparation process, good SERS enhancement and affordable materials (PET, Cu, Ag and GO, etc.), this substrate presents high cost performance and a promising application prospect.