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.

Charge-transfer-driven ultrasensitive SERS sensing in a two-dimensional titanium carbonitride MXene.

Two-dimensional (2D) MXenes stand out as promising platforms for surface-enhanced Raman scattering (SERS) sensing owing to their metallic feature, various compositions, high surface area, compatibility with functionalization, and ease of fabrication. In this work, we report a high-performance 2D titanium carbonitride (Ti3CN) MXene SERS substrate. We reveal that the abundant electronic density of states near the Fermi level of Ti3CN MXene boosts the efficiency of photo-induced charge transfer at the interface of Ti3CN/molecule, resulting in significant Raman enhancement. The SERS sensitivity of Ti3CN MXene is further promoted through a 2D morphology regulation and molecular enrichment strategies. Moreover, prohibited drugs are detectable on this substrate, presenting the potential of trace-amount analysis on Ti3CN MXene. This work provides a deep insight of the SERS mechanisms of Ti3CN MXene and broadens the practical application of transition metal carbonitride MXene SERS substrates.

Photoinduced Charge Transfer Empowers Ta4C3 and Nb4C3 MXenes with High SERS Performance.

This study introduces two-dimensional (2D) Ta4C3 and Nb4C3 MXenes as outstanding materials for surface-enhanced Raman scattering (SERS) sensing, marking a significant departure from traditional noble-metal substrates. These MXenes exhibit exceptional SERS capabilities, achieving enhancement factors around 105 and detection limits as low as 10-7 M for various analytes, including environmental pollutants and drugs. The core of their SERS functionality is attributed to the robust interfacial photoinduced charge-transfer interactions between the MXenes and the adsorbed molecules. This deep insight not only advances our understanding of MXene materials in SERS applications but also opens new avenues for developing highly sensitive and selective SERS sensors. The potential of Ta4C3 and Nb4C3 MXenes to revolutionize SERS technology underscores their importance in environmental monitoring, food safety, and beyond.

Alloy Engineering Allows On-Demand Design of Ultrasensitive Monolayer Semiconductor SERS Substrates.

The chemical mechanism (CM) of surface-enhanced Raman scattering (SERS) has been recognized as a decent approach to mildly amplify Raman scattering. However, the insufficient charge transfer (CT) between the SERS substrate and molecules always results in unsatisfying Raman enhancement, exerting a substantial restriction for CM-based SERS. In principle, CT is dominated by the coupling between the energy levels of a semiconductor-molecule system and the laser wavelength, whereas precise tuning of the energy levels is intrinsically difficult. Herein, two-dimensional transition-metal dichalcogenide alloys, whose energy levels can be precisely and continuously tuned over a wide range by simply adjusting their compositions, are investigated. The alloys enable on-demand construction of the CT resonance channels to cater to the requirements of a specific target molecule in SERS. The SERS signals are highly reproducible, and a clear view of the SERS dependences on the energy levels is revealed for different CT resonance terms.

Verification and Analysis of Single-Molecule SERS Events via Polarization-Selective Raman Measurement.

We propose polarization-selective Raman measurement as a decent method for single-molecule surface-enhanced Raman scattering (SMSERS) verification. This approach features rapid acquisition of SMSERS events and appeals liberal requirements for analyte concentration. It is demonstrated as an efficient tool in sorting out dozens of SMSERS events from a large-scale plasmonic dimer array. In addition, it allows identification of a mixed SMSERS event containing two different individual molecules. In this article, the RPM method is employed to explore the underlying mechanisms of signal blinking, spectral wandering, and other unique characteristics in SMSERS. We observed synchronized blinking of different modes from one Rhodamine 6G (R6G) molecule, but a disagreement is found in a mixed SMSERS event containing one R6G molecule and one crystal violet molecule. Our approach offers a reliable means to interpret SMSERS events in statistical terms and facilitate the fundamental understanding of SMSERS.

Inkjet-printed paper-based semiconducting substrates for surface-enhanced Raman spectroscopy.

As a powerful analytical tool of molecular detection, surface-enhanced Raman spectroscopy (SERS) has attracted great attention in varied fields. However, it has seriously impeded the development of SERS that the preparation process is generally complicated and traditional substrates lack eco-friendliness, economy and flexibility. Herein, we fabricated the inkjet-printed paper-based semiconducting SERS substrates for the first time via an inexpensive office inkjet printer with representative two-dimensional MoO3-x nanosheets ink. Compared with conventional substrates, these paper-based semiconducting substrates not only could meet the requirements of simple and large-scale preparation, but also realize efficient sample collection by merely swabbing the surface. We obtained the detection limit concentration of rhodamine 6G as low as 10-7 M. Furthermore, these flexible paper-based substrates were successfully applied to detect crystal violet and malachite green on the fish surface by swabbing. With immense potentiality in practical applications, the inkjet-printed paper-based semiconducting SERS substrates are expected to open a new prospect for SERS.

Ultrasonic exfoliated ReS2 nanosheets: fabrication and use as co-catalyst for enhancing photocatalytic efficiency of TiO2 nanoparticles under sunlight.

Rhenium disulfide (ReS2) is an interesting kind of transition metal dichalcogenide (TMD) because of its thickness-independent and suitable direct-bandgap structure, which could enable highly efficient solar-energy conversion efficiency. Here, we demonstrate an ultrasonic liquid exfoliation technique in combination with grinding to produce high quality ReS2 nanosheets (NSs) on a large scale. After combination with TiO2 nanoparticles, the co-catalytic performance of TiO2@ReS2 nanocomposites is investigated, which presents dramatically enhanced degradation activity of organic pigments under sunlight illumination in comparison with pure TiO2 nanoparticles. The underlying mechanism of enhanced photocatalytic activity can be attributed to improved separation efficiency of photogenerated electron-hole pairs in TiO2@ReS2 nanocomposites, which is confirmed by photoluminescence analysis and photoelectrochemical measurements. Our results demonstrate that the layered ReS2 NS is a promising two-dimensional supporting platform for photocatalysis and moreover it could also provide a new perspective on TMDs co-catalyst.

Plasmon-coupled charge transfer in WO3-x semiconductor nanoarrays: toward highly uniform silver-comparable SERS platforms.

Transition metal oxide semiconductors have been explored in surface-enhanced Raman scattering (SERS) active substrates, yet their detection sensitivity and enhancement effects are inferior. What's more, the reported fabrication technique ignored the effects of the electromagnetic mechanisms and was far from satisfactory for practical applications. Herein, we report on a convenient nanotechnique to fabricate large-area hexagon plum-blossom-like WO3-x nanoarrays based on aluminum nanobowl array substrates. Localized surface plasmon resonance can be increased via adjusting the time of tungsten magnetron sputtering with H2 annealing treatment. The introduction of a double-switch experiment demonstrates that localized surface plasmon-coupled photoinduced charge transfer can not only increase SERS enhancement comparable to similar silver nanostructures but also implement a low limit of detection below 10-9 M. A triple-switch experiment offers specific rules in the molecular detection of WO3-x semiconductors and important guidance for the fabrication of SERS-active semiconducting platforms.

Facile design of ultra-thin anodic aluminum oxide membranes for the fabrication of plasmonic nanoarrays.

Ultra-thin anodic aluminum oxide (AAO) membranes are efficient templates for the fabrication of patterned nanostructures. Herein, a three-step etching method to control the morphology of AAO is described. The morphological evolution of the AAO during phosphoric acid etching is systematically investigated and a nonlinear growth mechanism during unsteady-state anodization is revealed. The thickness of the AAO can be quantitatively controlled from ∼100 nm to several micrometers while maintaining the tunablity of the pore diameter. The AAO membranes are robust and readily transferable to different types of substrates to prepare patterned plasmonic nanoarrays such as nanoislands, nanoclusters, ultra-small nanodots, and core-satellite superstructures. The localized surface plasmon resonance from these nanostructures can be easily tuned by adjusting the morphology of the AAO template. The custom AAO template provides a platform for the fabrication of low-cost and large-scale functional nanoarrays suitable for fundamental studies as well as applications including biochemical sensing, imaging, photocatalysis, and photovoltaics.

Self-assembled bundled TiO2 nanowire arrays encapsulated with indium tin oxide for broadband absorption in plasmonic photocatalysis.

In order to enhance photocatalysis by broadening light harvesting, bundled TiO2 nanowire bundle arrays are encapsulated with indium tin oxide (ITO) by a self-assembly technique involving anodization, electrochemical etching, and ITO deposition. The plasmonic photocatalyst, which has a multiscale structure with variable nanoscale gaps as well as microscale funnels, shows broadband localized surface plasmon resonance absorption of 84% in the wavelength range between 400 and 2500 nm. The improved photocatalytic efficiency is demonstrated by methyl orange degradation under sunlight illumination. The improvement stems from enhanced light harvesting arising from the localized surface plasmon resonance of the ITO membrane which extends the light response to the visible and NIR regions and excites hot charge carriers.

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

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive surface analysis technique that is widely used in chemical sensing, bioanalysis, and environmental monitoring. The design of the SERS substrates is crucial for obtaining high-quality SERS signals. Recently, 2D transition metal dichalcogenides (2D TMDs) have emerged as high-performance SERS substrates due to their superior stability, ease of fabrication, biocompatibility, controllable doping, and tunable bandgaps and excitons. In this review, a systematic overview of the latest advancements in 2D TMDs SERS substrates is provided. This review comprehensively summarizes the candidate 2D TMDs SERS materials, elucidates their working principles for SERS, explores the strategies to optimize their SERS performance, and highlights their practical applications. Particularly delved into are the material engineering strategies, including defect engineering, alloy engineering, thickness engineering, and heterojunction engineering. Additionally, the challenges and future prospects associated with the development of 2D TMDs SERS substrates are discussed, outlining potential directions that may lead to significant breakthroughs in practical applications.

Mechanism Switch in Surface-Enhanced Raman Scattering: The Role of Nanoparticle Dimensions.

Surface-enhanced Raman scattering (SERS) is renowned for amplifying Raman signals, with electromagnetic mechanism (EM) enhancement arising from localized surface plasmon resonances and chemical mechanism (CM) enhancement as a result of charge transfer interactions. Despite the conventional emphasis on EM as a result of plasmonic effects, recent findings highlight the significance of CM when noble metals appear as smaller entities. However, the threshold size of the noble metal clusters/particles corresponding to the switch in SERS mechanisms is not clear at present. In this work, the VSe2-xOx/Au composites with different Au sizes are employed, in which a clear view of the SERS mechanism switch is observed at the Au size range of 16-21 nm. Our findings not only provide insight into the impact of noble metal size on SERS efficiency but also offer quantitative data to assist researchers in making informed judgments when analyzing SERS mechanisms.

Plasmonic trimers designed as SERS-active chemical traps for subtyping of lung tumors.

Plasmonic materials can generate strong electromagnetic fields to boost the Raman scattering of surrounding molecules, known as surface-enhanced Raman scattering. However, these electromagnetic fields are heterogeneous, with only molecules located at the 'hotspots', which account for ≈ 1% of the surface area, experiencing efficient enhancement. Herein, we propose patterned plasmonic trimers, consisting of a pair of plasmonic dimers at the bilateral sides and a trap particle positioned in between, to address this challenge. The trimer configuration selectively directs probe molecules to the central traps where 'hotspots' are located through chemical affinity, ensuring a precise spatial overlap between the probes and the location of maximum field enhancement. We investigate the Raman enhancement of the Au@Al2O3-Au-Au@Al2O3 trimers, achieving a detection limit of 10-14 M of 4-methylbenzenethiol, 4-mercaptopyridine, and 4-aminothiophenol. Moreover, single-molecule SERS sensitivity is demonstrated by a bi-analyte method. Benefiting from this sensitivity, our approach is employed for the early detection of lung tumors using fresh tissues. Our findings suggest that this approach is sensitive to adenocarcinoma but not to squamous carcinoma or benign cases, offering insights into the differentiation between lung tumor subtypes.

High-specificity molecular sensing on an individual whispering-gallery-mode cavity: coupling-enhanced Raman scattering by photoinduced charge transfer and cavity effects.

Optical whispering-gallery-mode (WGM) cavities have gained considerable interest because of their unique properties of enhanced light-matter interactions. Conventional WGM sensing is based on the mechanisms of mode shift, mode broadening, or mode splitting, which requires a small mode volume and an ultrahigh Q-factor. Besides, WGM sensing suffers from a lack of specificity in identifying substances, and additional chemical functionalization or incorporation of plasmonic materials is required for achieving good specificity. Herein, we propose a new sensing method based on an individual WGM cavity to achieve ultrasensitive and high-specificity molecular sensing, which combines the features of enhanced light-matter interactions on the WGM cavity and the "fingerprint spectrum" of surface-enhanced Raman scattering (SERS). This method identifies the substance by monitoring the Raman signal enhanced by the WGM cavity rather than monitoring the variation of the WGM itself. Therefore, ultrasensitive and high-specificity molecular sensing can be accomplished even on a low-Q cavity. The working principles of the proposed sensing method were also systematically investigated in terms of photoinduced charge transfer, Purcell effect, and optical resonance coupling. This work provides a new WGM sensing approach as well as a strategy for the design of a high-performance SERS substrate by creating an optical resonance mode.

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.

Monolayer Iron Oxychloride with a Resonant Band Structure for Ultrasensitive Molecular Sensing.

Two-dimensional layered materials (2DLMs) are expected to be next-generation commercial sensors for surface-enhanced Raman scattering (SERS) sensing owing to their unique structural features and physicochemical properties. The low sensitivity and poor universality of 2DLMs are the dominant barriers toward their practical applications. Herein, we report that monolayer iron oxychloride (FeOCl) with a naturally suitable band structure is a promising candidate for ultrasensitive SERS sensing. The generally boosted Raman scattering cross section of different analyte-FeOCl systems benefits from the resonant photoinduced charge transfer processes and strong ground-state interactions. In addition, the strong adsorption ability of monolayer FeOCl is crucial for rapid detection in practical applications, which is proven to be much better than those of conventional SERS sensors. Consequently, monolayer FeOCl enables diverse SERS applications, including multicomponent analysis, chemical reaction monitoring, and indirect ion sensing.

Two-dimensional MBenes with ordered metal vacancies for surface-enhanced Raman scattering.

As an emerging class of two-dimensional (2D) materials, MBenes show enormous potential for optoelectronic applications. However, their use in molecular sensing as surface-enhanced Raman scattering (SERS)-active material is unknown. Herein, for the first time, we develop a brand-new high-performance MBene SERS platform. Ordered vacancy-triggered highly sensitive SERS platform with outstanding signal uniformity based on a 2D Mo4/3B2 MBene material was designed. The 2D Mo4/3B2 MBene presented superior SERS activity to most of the semiconductor SERS substrates, showing a remarkable Raman enhancement factor of 3.88 × 106 and an ultralow detection limit of 1 × 10-9 M. The underlying SERS mechanism is revealed from systematic experiments and density functional theory calculations that the ultrahigh SERS sensitivity of 2D Mo4/3B2 MBene is derived from the efficient photoinduced charge transfer process between MBene substrates and adsorbed molecules. The abundant electronic density of states near the Fermi level of 2D Mo4/3B2 MBene enables its Raman enhancement by a factor of 100 000 times higher than that of the bulk MoB. Consequently, the 2D Mo4/3B2 MBene could accurately detect various trace chemical analytes. Moreover, with ordered metal vacancies in the 2D Mo4/3B2 MBene, uniform charge transfer sites are formed, resulting in an outstanding signal uniformity with a relative standard deviation down to 6.0%. This work opens up a new horizon for the high-performance SERS platform based on MBene materials, which holds great promise in the field of chemical sensing.

Flexible two-dimensional MXene-based antennas.

With the growing development of the Internet of things, wearable electronic devices have been extensively applied in civilian and military fields. As an essential component of data transmission in wearable electronics, a flexible antenna is one of the key aspects of research. Conventional metal antennas suffer from a large skin depth, and cannot satisfy the requirements of wearable electronics such as light weight, flexibility, and thinness. Recently, a group of two-dimensional metallic metal carbides (named MXenes) have been explored as building blocks for high-performance flexible antennas with excellent flexibility and superior mechanical strength. The appearance of hydrophilic functional groups at the surface of a MXene allows simple, scalable, and environmentally friendly manufacturing of MXene-based antennas. In this minireview, some pioneering works of MXene-based flexible radio frequency components are summarized, and the existing bottlenecks and the future trends of this promising field are discussed.

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.

Flexible Two-Dimensional Vanadium Carbide MXene-Based Membranes with Ultra-Rapid Molecular Enrichment for Surface-Enhanced Raman Scattering.

Two-dimensional (2D) MXene materials have attracted broad interest in surface-enhanced Raman scattering (SERS) applications by virtue of their abundant surface terminations and excellent photoelectric properties. Herein, we propose to design highly sensitive MXene-based SERS membranes by integrating a 2D downsizing strategy with molecular enrichment approaches. Two types of 2D vanadium carbide (V4C3 and V2C) MXenes are demonstrated for ultrasensitive SERS sensing, and corresponding SERS mechanisms including the effect of 2D vanadium carbide thickness on their electron density states and interfacial photoinduced charge transfer resonance were discussed. A 2D downsizing strategy authorizes nonplasmonic SERS detection with a sensitivity of 1 × 10-7 M. Moreover, the performance can be further upgraded by vacuum-assisted filtration, which enables an ultrarapid molecular enrichment (within 2 min), ultrahigh molecular removal rate (over 95%), and improved sensitivity (5 × 10-9 M). This work may shed light on the MXene-based materials as an innovative platform for nonplasmonic SERS detection.