Surface-enhanced Raman spectroscopy (SERS), a sensitive analytical technique that has single molecular sensitivity, has attracted continuous attention for both application and academic research. Semiconductor-based substrates with SERS activity present more practical applications, ranging from surface science to biological detection because of their lower cost and better biocompatibility compared with noble metals. However, the SERS performance of most semiconductor-based substrates is not significant. Herein, we propose the concept of semiconductor heterojunction-enhanced Raman scattering and design a vertical nanothickness heterojunction of W18O49/monolayer MoS2. As a result, the Raman signals of analyte Rhodamine 6G are detectable even with an ultralow concentration of 10–9 M on W18O49/monolayer MoS2 substrates. The enhancement factor is around 3.45 × 107. We confirmed from experiments and theory that the coupling of these two semiconductor materials could lead to dramatic enhancement of photoinduced charge-transfer processes, which enables giant heterojunction-enhanced Raman scattering.
Exploring the influence of interlayer interaction on SERS performance by using 2D PtSe2 and ReS2 with different numbers of layers as the research objects.
Surface-enhanced Raman scattering (SERS) is recognized as one of the most sensitive spectroscopic tools for chemical and biological detections. Hotspots engineering has expedited promotion of SERS performance over the past few decades. Recently, molecular enrichment has proven to be another effective approach to improve the SERS performance. In this work, we propose a concept of “motile hotspots” to realize ultrasensitive SERS sensing by combining hotspots engineering and active molecular enrichment. High-density plasmonic nanostructure-supporting hotspots are assembled on the tubular outer wall of micromotors via nanoimprint and rolling origami techniques. The dense hotspots carried on these hierarchically structured micromotors (HSMs) can be magnet-powered to actively enrich molecules in fluid. The active enrichment manner of HSMs is revealed to be effective in accelerating the process of molecular adsorption. Consequently, SERS intensity increases significantly because of more molecules being adjacent to the hotspots after active molecular enrichment. This “motile hotspots” concept provides a synergistical approach in constructing a SERS platform with high performance. Moreover, the newly developed construction method of HSMs manifests the possibility of tailoring tubular length and diameter as well as surface patterns on the outer wall of HSMs, demonstrating good flexibility in constructing customized micromotors for various applications.
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 4bromothiophenol (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.
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.
The plasmonic metal/semiconductor heterojunction provides a unique paradigm for manipulating light to improve the efficiency of plasmonic materials. Previous studies suggest that the improvement originates from the enhanced carrier exchanges between the plasmonic component of the heterojunction and molecules. This viewpoint, known as the chemical mechanism, is reasonable but insufficient, because the construction of the heterojunction will lead to a charge redistribution in the plasmonic component and cause changes in its physical characteristics. Herein, we will try to clarify that these changes are decisive factors in specific applications by investigating the surface-enhanced Raman scattering (SERS) behavior of a typical Ag/TiO 2 heterojunction. We observed significant changes in SERS spectra by modulating the band alignment of the heterojunction in a loop. Identical trends in SERS spectra were observed despite the fact that the charge transfer from the heterojunction to molecules was blocked, suggesting that the major SERS enhancement originates from electromagnetic mechanisms rather than chemical ones.
Multifunctional devices based on 2D organic/inorganic van der Waals heterostructures (2D OIHs) exhibit excellent properties due to extensive and flexible structural tunability. However, how to precisely regulate devices via in situ monitoring technique remains a great challenge, and corresponding development is still in its infancy. In this Letter, we show that Raman spectroscopy can serve as an effective in situ detection strategy to systematically observe the interfacial electron–phonon coupling (IEPC) between substrate and 2D OIHs. Combining non-adiabatic molecular dynamics simulations with ultrafast spectroscopy, we reveal that the different strengths of IEPC between substrates and 2D OIHs can directly modulate the photocarrier lifetimes of inorganic 2D materials, and therefore, indirectly modify the Raman-sensitive photo-induced charge transfer processes at the interface of 2D OIHs. Further in situ Raman evidence demonstrates the unique advantage of Raman spectroscopy with high sensitivity to monitor different substrate-induced IEPC under variable temperature.
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.
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