Can Copper Nanostructures Sustain High-Quality Plasmons?

Silver, king among plasmonic materials, features low inelastic absorption in the visible-infrared (vis-IR) spectral region compared to other metals. In contrast, copper is commonly regarded as too lossy for actual applications. Here, we demonstrate vis-IR plasmons with quality factors >60 in long copper nanowires (NWs), as determined by electron energy-loss spectroscopy. We explain this result by noticing that most of the electromagnetic energy in these plasmons lies outside the metal, thus becoming less sensitive to inelastic absorption. Measurements for silver and copper NWs of different diameters allow us to elucidate the relative importance of radiative and nonradiative losses in plasmons spanning a wide spectral range down to <20 meV. Thermal population of such low-energy modes becomes significant and generates electron energy gains associated with plasmon absorption, rendering an experimental determination of the NW temperature. Copper is therefore emerging as an attractive, cheap, abundant material platform for high-quality plasmonics in elongated nanostructures.

Flexible Free-Standing MoO3/Ti3C2T z MXene Composite Films with High Gravimetric and Volumetric Capacities.

Enhancing both the energy storage and power capabilities of electrochemical capacitors remains a challenge. Herein, Ti3C2T z MXene is mixed with MoO3 nanobelts in various mass ratios and the mixture is used to vacuum filter binder free, open, flexible, and free-standing films. The conductive Ti3C2T z flakes bridge the nanobelts, facilitating electron transfer; the randomly oriented, and interconnected, MoO3 nanobelts, in turn, prevent the restacking of the Ti3C2T z nanosheets. Benefitting from these advantages, a MoO3/Ti3C2T z film with a 8:2 mass ratio exhibits high gravimetric/volumetric capacities with good cyclability, namely, 837 C g-1 and 1836 C cm-3 at 1 A g-1 for an ≈ 10 µm thick film; and 767 C g-1 and 1664 C cm-3 at 1 A g-1 for ≈ 50 µm thick film. To further increase the energy density, hybrid capacitors are fabricated with MoO3/Ti3C2T z films as the negative electrodes and nitrogen-doped activated carbon as the positive electrodes. This device delivers maximum gravimetric/volumetric energy densities of 31.2 Wh kg-1 and 39.2 Wh L-1, respectively. The cycling stability of 94.2% retention ratio after 10 000 continuous charge/discharge cycles is also noteworthy. The high energy density achieved in this work can pave the way for practical applications of MXene-containing materials in energy storage devices.

Interface Interactions in Conjugated Polymer Composite with Metal Oxide Nanoparticles.

This study presents the preparation, characterization, and properties of a new composite containing cerium oxide nanoparticles and a conjugated polymer. CeO2 nanoparticles prepared using the co-precipitation method were dispersed into the conjugated polymer, prepared using the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. The interface interactions between the two components and the resultant optoelectronic properties of the composite are demonstrated. According to transmission electron microscopy and X-ray absorption spectroscopy, the dispersion of CeO2 nanoparticles in the polymer matrix strongly depends on the CeO2 nanoparticle concentration and results in different degrees of charge transfer. The photo-induced charge transfer and recombination processes were studied using steady-state optical spectroscopy, which shows a significant fluorescence quenching and red shifting in the composite. The higher photo-activity of the composite as compared to the single components was observed and explained. Unexpected room temperature ferromagnetism was observed in both components and all composites, of which the origin was attributed to the topology and defects.

Magnetism and plasmonic performance of mesoscopic hollow ceria spheres decorated with silver nanoparticles.

We investigate the role of interfaces and surfaces in the magnetic and surface enhanced Raman spectroscopy (SERS) properties of CeO2 hollow spheres decorated with Ag nanoparticles (H-CeO2@Ag). The composites, H-CeO2@Ag, were synthesized using a newly developed two-step process. The CeO2 hollow sphere diameter ranges from 100 nm to 2 µm and the grafted Ag nanoparticle (NP) size varies from 5 to 50 nm with a controllable coverage ratio. Spectroscopic and microscopic characterization confirms the formation of an interface between the Ag and ceria and shows different charge rearrangements occurring at both the interface and the surface. Room temperature ferro-magnetism was observed in all composites, and is associated mostly with ceria surface defects. A strong SERS effect was reported with a detection limit down to 10-14 M for the rhodamine 6G analyte. Scanning transmission electron microscopy and electron energy loss spectroscopy investigation reveals that hot-spots are associated with the silver NP surfaces and also with the Ag/CeO2 interface. This interfacial hot spot occurs for metallic particles above 30 nm and is strongly red shifted with respect to the Ag surface plasmon. The strong SERS activity is then attributed to the presence of several types of hot-spots and the geometrical features (buoyant hollow sphere and size dispersion) of the composite.

Surface engineered doping of hematite nanorod arrays for improved photoelectrochemical water splitting.

Given the narrow band gap enabling excellent optical absorption, increased charge carrier density and accelerated surface oxidation reaction kinetics become the key points for improved photoelectrochemical performances for water splitting over hematite (α-Fe2O3) photoanodes. In this study, a facile and inexpensive method was demonstrated to develop core/shell structured α-Fe2O3 nanorod arrays. A thin, Ag-doped overlayer of ~2-3 nm thickness was formed along α-Fe2O3 nanorods via ultrasonication treatment of solution-based ß-FeOOH nanorods in Ag precursor solution followed by high temperature annealing. The obtained α-Fe2O3/AgxFe2-xO3 core/shell nanorod films demonstrated much higher photoelectrochemical performances as photoanodes than the pristine α-Fe2O3 nanorod film, especially in the visible light region; the incident photon-to-current efficiency (IPCE) at 400 nm was increased from 2.2% to 8.4% at 1.23 V vs. RHE (Reversible hydrogen electrode). Mott-Schottky analysis and X-ray absorption spectra revealed that the Ag-doped overlayer not only increased the carrier density in the near-surface region but also accelerated the surface oxidation reaction kinetics, synergistically contributing to the improved photoelectrochemical performances. These findings provide guidance for the design and optimization of nanostructured photoelectrodes for efficient solar water splitting.