Plasmonic nanomaterials coupled with catalytically active surfaces can provide unique opportunities for various catalysis applications, where surface plasmons produced upon proper light excitation can be adopted to drive and/or facilitate various chemical reactions. A brief introduction to the localized surface plasmon resonance and recent design and fabrication of highly efficient plasmonic nanostructures, including plasmonic metal nanostructures and metal/semiconductor heterostructures is given. Taking advantage of these plasmonic nanostructures, the following highlights summarize recent advances in plasmon‐driven photochemical reactions (coupling reactions, O2 dissociation and oxidation reactions, H2 dissociation and hydrogenation reactions, N2 fixation and NH3 decomposition, and CO2 reduction) and plasmon‐enhanced electrocatalytic reactions (hydrogen evolution reaction, oxygen reduction reaction, oxygen evolution reaction, alcohol oxidation reaction, and CO2 reduction). Theoretical and experimental approaches for understanding the underlying mechanism of surface plasmon are discussed. A proper discussion and perspective of the remaining challenges and future opportunities for plasmonic nanomaterials and plasmon‐related chemistry in the field of energy conversion and storage is given in conclusion.
2D transition metal dichalcogenide (TMD) materials have been recognized as active platforms for surface‐enhanced Raman spectroscopy (SERS). Here, the effect of crystal structure (phase) transition is shown, which leads to altered electronic structures of TMD materials, on the Raman enhancement. Using thermally evaporated copper phthalocyanine, solution soaked rhodamine 6G, and crystal violet as typical probe molecules, it is found that a phase transition from 2H‐ to 1T‐phase can significantly increase the Raman enhancement effect on MoX2 (X = S, Se) monolayers through a predominantly chemical mechanism. First‐principle density functional theory calculations indicate that the significant enhancement of the Raman signals on metallic 1T‐MoX2 can be attributed to the facilitated electron transfer from the Fermi energy level of metallic 1T‐MoX2 to the highest occupied molecular orbital level of the probe molecules, which is more efficient than the process from the top of valence band of semiconducting 2H‐MoX2. This study not only reveals the origin of the Raman enhancement and identifies 1T‐MoSe2 and 1T‐MoS2 as potential Raman enhancement substrates, but also paves the way for designing new 2D SERS substrates via phase‐transition engineering.
Light-induced halide segregation limits the bandgap tunability of mixed-halide perovskites for tandem photovoltaics. Here we report that light-induced halide segregation is strain-activated in MAPb(I1−xBrx)3 with Br concentration below approximately 50%, while it is intrinsic for Br concentration over approximately 50%. Free-standing single crystals of CH3NH3Pb(I0.65Br0.35)3 (35%Br) do not show halide segregation until uniaxial pressure is applied. Besides, 35%Br single crystals grown on lattice-mismatched substrates (e.g. single-crystal CaF2) show inhomogeneous segregation due to heterogenous strain distribution. Through scanning probe microscopy, the above findings are successfully translated to polycrystalline thin films. For 35%Br thin films, halide segregation selectively occurs at grain boundaries due to localized strain at the boundaries; yet for 65%Br films, halide segregation occurs in the whole layer. We close by demonstrating that only the strain-activated halide segregation (35%Br/45%Br thin films) could be suppressed if the strain is properly released via additives (e.g. KI) or ideal substrates (e.g. SiO2).
2D transition metal dichalcogenides materials are explored as potential surface-enhanced Raman spectroscopy substrates. Herein, a systematic study of the Raman enhancement mechanism on distorted 1T (1T') rhenium disulfide (ReS ) nanosheets is demonstrated. Combined Raman and photoluminescence studies with the introduction of an Al O dielectric layer unambiguously reveal that Raman enhancement on ReS materials is from a charge transfer process rather than from an energy transfer process, and Raman enhancement is inversely proportional while the photoluminescence quenching effect is proportional to the layer number (thickness) of ReS nanosheets. On monolayer ReS film, a strong resonance-enhanced Raman scattering effect dependent on the laser excitation energy is detected, and a detection limit as low as 10 m can be reached from the studied dye molecules such as rhodamine 6G and methylene blue. Such a high enhancement factor achieved through enhanced charge interaction between target molecule and substrate suggests that with careful consideration of the layer-number-dependent feature and excitation-energy-related resonance effect, ReS is a promising Raman enhancement platform for sensing applications.
Self-assembled organic-inorganic CH3NH3PbI3 perovskite microwires (MWs) upon humidity exposure along several weeks were investigated by photoluminescence (PL) spectroscopy, Raman spectroscopy, and X-ray diffraction (XRD). We show that, in addition to the common perovskite decomposition into PbI2 and the formation of a hydrated phase, humidity induced a gradual PL redshift at the initial weeks that is stabilized for longer exposure (~ 21 nm over the degradation process) and an intensity enhancement. Original perovskite Raman band and XRD reflections slightly shifted upon humidity, indicating defects formation and structure distortion of the MWs crystal lattice. By correlating the PL, Raman, and XRD results, it is believed that the redshift of the MWs PL emission was originated from the structural disorder caused by the incorporation of H2O molecules in the crystal lattice and radiative recombination through moisture-induced subgap trap states. Our study provides insights into the optical and structural response of organic-inorganic perovskite materials upon humidity exposure.Electronic supplementary materialThe online version of this article (10.1186/s11671-018-2470-0) contains supplementary material, which is available to authorized users.
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