Surface-enhanced Raman scattering (SERS) is a powerful spectroscopy technique that can provide non-destructive and ultra-sensitive characterization down to single molecular level, comparable to single-molecule fluorescence spectroscopy. However, generally substrates based on metals such as Ag, Au and Cu, either with roughened surfaces or in the form of nanoparticles, are required to realise a substantial SERS effect, and this has severely limited the breadth of practical applications of SERS. A number of approaches have extended the technique to non-traditional substrates, most notably tip-enhanced Raman spectroscopy (TERS) where the probed substance (molecule or material surface) can be on a generic substrate and where a nanoscale gold tip above the substrate acts as the Raman signal amplifier. The drawback is that the total Raman scattering signal from the tip area is rather weak, thus limiting TERS studies to molecules with large Raman cross-sections. Here, we report an approach, which we name shell-isolated nanoparticle-enhanced Raman spectroscopy, in which the Raman signal amplification is provided by gold nanoparticles with an ultrathin silica or alumina shell. A monolayer of such nanoparticles is spread as 'smart dust' over the surface that is to be probed. The ultrathin coating keeps the nanoparticles from agglomerating, separates them from direct contact with the probed material and allows the nanoparticles to conform to different contours of substrates. High-quality Raman spectra were obtained on various molecules adsorbed at Pt and Au single-crystal surfaces and from Si surfaces with hydrogen monolayers. These measurements and our studies on yeast cells and citrus fruits with pesticide residues illustrate that our method significantly expands the flexibility of SERS for useful applications in the materials and life sciences, as well as for the inspection of food safety, drugs, explosives and environment pollutants.
Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel‐cell‐relevant reaction. The electrocatalyst consists of PdxAg alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible‐light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the PdxAg NTs.
An homologous series of divinylchalcogenophene‐bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(µ‐CH=CH‐C4H2E‐CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X‐ray crystallography and various spectroscopic techniques. The single‐crystal X‐ray diffraction results reveal a distinct short/long bond‐length alternation along the polyene‐like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five‐membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one‐electron oxidation processes, the half‐wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re‐organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene‐like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10‐atom Ru–[4‐s‐cis‐all‐trans‐(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.
For a period of time, the O2 cathode has been the focus of the researches, while the study on lithium anode and their interactions is quite rare in rechargeable lithium-oxygen...
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