Plasmonic Heterostructure TiO2‐MCs/WO3−x‐NWs with Continuous Photoelectron Injection Boosting Hot Electron for Methane Generation

Nonmetallic plasmonic heterostructure TiO₂‐mesocrystals/WO_3?x‐nanowires (TiO₂‐MCs/WO_3?x‐NWs) are constructed by coupling mesoporous crystal TiO₂ and plasmonic WO_3?x through a solvothermal procedure. The continuous photoelectron injection from TiO₂ stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO_3?x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO₂‐MCs/WO_3?x‐NWs is attributed to plasmonic hot electrons excited on WO_3?x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO_3?x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO₂‐MCs/WO_3?x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO₂ reduction, which exhibit much higher activity (16.3 µmol g^?1 h^?1) and selectivity (83%) than TiO₂‐MCs (3.5 µmol g^?1 h^?1, 42%) and WO_3?x‐NWs (8.0 µmol g^?1 h^?1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO₂ to WO_3?x, and the nonmetallic SPR of WO_3?x plays a great role in the highly selective methane generation during CO₂ photoreduction.     

Near‐Infrared Plasmonic 2D Semimetals for Applications in Communication and Biology

Localized surface plasmon resonance (LSPR) has many applications which require meeting specific wavelength windows. The most prominent examples are photothermal therapy in biology, matched to the biological window (650–1350 nm), and communication relying on photodetection in optoelectronics, matched to the communication window (1260–1675 nm). However, for the classic noble metals (Au, Ag), tuning LSPRs from visible region to these two windows is still a demanding task due to their intrinsic limitations on charge density and dielectric function. Here, the discovery of near‐infrared biological and communication window‐matched plasmonic properties of semimetal TiS₂ nanosheets (NSs) is reported for the first time. Developed synthesis procedures allow fine‐tuning width and thickness of single‐crystal TiS₂ NSs. During characterization a new and intensive absorption peak in the 1000–1400 nm range is observed from both TiS₂ NS colloid solutions and films. This peak is attributed to LSPR due to its dependence on particle shape and on the refractive index of solvents. The superiority of such LSPRs is demonstrated in both, biological and optical applications: excitation at 808 and 980 nm generates a ≈50 °C photothermal temperature rise, while excitation at 1310 nm results in two‐times enhanced photocurrents of PbS photodetectors compared to untreated devices.     

Plasmonic Au/TiO2‐Dumbbell‐On‐Film Nanocavities for High‐Efficiency Hot‐Carrier Generation and Extraction

Plasmon‐induced hot carriers have vast potential for light‐triggered high‐efficiency carrier generation and extraction, which can overcome the optical band gap limit of conventional semiconductor‐based optoelectronic devices. Here, it is demonstrated that Au/TiO₂ dumbbell nanostructures assembled on a thin Au film serve as an efficient optical absorber and a hot‐carrier generator in the visible region. Upon excitation of localized surface plasmons in such coupled particle‐on‐film nanocavities, the energetic conduction electrons in Au can be injected over the Au/TiO₂ Schottky barrier and migrated to TiO₂, participating in the chemical reaction occurring at the TiO₂ surface. Compared with the same dumbbell nanostructures on an indium tin oxide (ITO) film, such nanocavities exhibit remarkable enhancement in both photocurrent amplitude and reaction rate that arise from increased light absorption and near‐field amplification in the presence of the Au film. The incident‐wavelength‐dependent photocurrent and reaction rate measurements jointly reveal that Au‐film‐mediated near‐field localization facilitates more efficient electron–hole separation and transport in the dumbbells and also promotes strong d‐band optical transitions in the Au film for generation of extra hot electrons. Such nanocavities provide a new plasmonic platform for effective photoexcitation and extraction of hot carriers and also better understanding of their fundamental science and technological implications in solar energy harvesting.     

Near‐Infrared SERS Nanoprobes with Plasmonic Au/Ag Hollow‐Shell Assemblies for In Vivo Multiplex Detection

For the effective application of surface‐enhanced Raman scattering (SERS) nanoprobes for in vivo targeting, the tissue transparency of the probe signals should be as high as it can be in order to increase detection sensitivity and signal reproducibility. Here, near‐infrared (NIR)‐sensitive SERS nanoprobes (NIR SERS dots) are demonstrated for in vivo multiplex detection. The NIR SERS dots consist of plasmonic Au/Ag hollow‐shell (HS) assemblies on the surface of silica nanospheres and simple aromatic Raman labels. The diameter of the HS interior is adjusted from 3 to 11 nm by varying the amount of Au³⁺ added, which results in a red‐shift of the plasmonic extinction of the Au/Ag nanoparticles toward the NIR (700–900 nm). The red‐shifted plasmonic extinction of NIR SERS dots causes enhanced SERS signals in the NIR optical window where endogenous tissue absorption coefficients are more than two orders of magnitude lower than those for ultraviolet and visible light. The signals from NIR SERS dots are detectable from 8‐mm deep in animal tissues. Three kinds of NIR SERS dots, which are injected into live animal tissues, produce strong SERS signals from deep tissues without spectral overlap, demonstrating their potential for in vivo multiplex detection of specific target molecules.     

Synthesis of Dumbbell‐Like Gold–Metal Sulfide Core–Shell Nanorods with Largely Enhanced Transverse Plasmon Resonance in Visible Region and Efficiently Improved Photocatalytic Activity

The metallic nanostructures with unique properties of tunable plasmon resonance and large field enhancement have been cooperated with semiconductor to construct hetero‐nanostructures for various applications. Herein, a general and facile approach to synthesize uniform dumbbell‐like gold–sulfide core–shell hetero‐nanostructures is reported. The transformation from Au nanorods (NRs) to dumbbell‐like Au NRs and coating of metal sulfide shells (including Bi₂S₃, CdS, Cu_xS, and ZnS) are achieved in a one‐pot reaction. Due to the reshaping of Au core and the deposition of sulfide shell, the plasmon resonances of Au NRs are highly enhanced, especially the about 2 times enhancement for the visible transverse plasmon resonance compared with the initial Au NRs. Owing to the highly enhanced visible light absorption and strong local electric field, we find the photocatalytic activity of dumbbell‐like Au–Bi₂S₃ NRs is largely enhanced compared with pure Bi₂S₃ and normal Au–Bi₂S₃ NRs by testing the photodegradation rate of Rhodamine B (RhB). Moreover, the second‐layer sulfide can be coated and the double‐shell Au–Bi₂S₃–CdS hetero‐nanostructures show further improved photodegradation rate, especially about 2 times than that of Degussa P25 TiO₂ (P25) ascribing to the optimum band arrangement and then the prolonged lifetime of photo‐generated carriers.