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At least 37 records · Page 2

Tunability and Long-Range Enhancement of Resonance Energy Transfer Facilitated by Plasmonic Nanorods

Resonance energy transfer (RET) between molecules or quantum dots is an important process in many energy-related applications. Different environmental structures have been studied and demonstrated to be able to enhance the RET rates between a nearby donor–acceptor pair. In particular, cylindrical silver nanorods and nanowires have shown an extraordinary ability to transfer energy along their longitudinal axes over large distances. However, the detailed mechanism of such transfer and the effects on the molecular RET process are as yet elusive. In this study, we use the recently developed computational tool based on the plasmon-coupled RET method to systematically study the effects of nanorods with different dimensions on the RET rates. We find that highly frequency-dependent coupling factor (CF) spectra, whose amplitudes determine RET rates, can be obtained due to the localized surface plasmon polariton modes of the rods with nanoscale dimensions. Simple phenomenological models can be derived for the wavelengths of CF peaks in relation to the length and width of the nanorods, providing easy tunability for enhancing the RET rate in specific wavelength ranges. When coupled to longer rods with mesoscale lengths, exponential decay of the CF over long donor–acceptor distances with a small decay constant is observed, leading to the possibility of long-range RET processes. Furthermore, drumhead resonance modes emerge on the flat ends of the rod when the rod’s diameter reaches 300 nm, resulting in extra enhancement to RET rate compared to certain thinner rods. Furthermore, these findings shed new light on the mechanism of plasmonic enhancement with silver nanorods and establish design principles for how to optimally utilize these structures to manipulate RET processes for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New insight into strain and composition of BaZrO 3 nanorods in REBCO superconductor

We report on strain and composition effects associated with growth of self-assembled BaZrO 3 (BZO) nanorods in REBa 2 Cu 3 O 7–δ (REBCO) superconductors (RE = rare earth = Y and Gd), which have a profound effect on flux pinning and in-field critical current performance. The a-b plane mismatch between BZO and REBCO is never fully coherently accommodated. Instead, the nanorods always assume a size at least one unit cell smaller than the corresponding 'hole' in the REBCO matrix, thus providing deep minima of in-plane mismatch strain. Next, we show that the nominal BZO nanorods are in fact solid solution Ba 2+ (Zr 4+ 1–z RE 3+ z )O 3–δ perovskite, thus strongly affecting the stoichiometry and relative amounts of REBCO and BZO. We demonstrate that by varying only the Ba content in the nominal composition of 15 mol.% BZO + REBCO, the unit cell density of BZO can be tuned from 5% to 23%, and the linear density of RE 2 O 3 (REO) precipitates from 18 to 1 μm –1 . Furthermore, the results explain the wide range of pinning performances observed for the same nominal amount of Zr addition and provide insight into the mechanisms behind the complex phenomenon of growth of nanorods by self-assembly in REBCO superconductors.

2G-HTS↗

Electrogenerated Chemiluminescence of Near-Infrared-Emitting CdSe@CdSe Nanorods in Aqueous Solution

Electrogenerated chemiluminescence (ECL) was observed from TOPO-capped CdSe@CdSe nanorods (NRs) depositing on a metal electrode in phosphate buffer solution (PBS). Two ECL peaks at -1.05 and -1.33 V in pH 9.2, 0.1 M PBS were found under cyclic voltammetric conditions. Cyclic voltammetry of this solution displayed no distinctive features, on the other hand, light emission was observed during cyclic potential scans. Additionally, the photoluminescence (PL) spectrum showed an emission maximum at 692 nm. The spectrum of ECL possesses one peak which coincides very well with the PL spectrum of the nanorods film. The mechanism for ECL peaks was proposed. Electron transfer reactions between charged nanorods and molecular redox-active coreactants such as dissolved oxygen and H2O2 or between positively and negatively charged nanorods occurred that led to electron and hole annihilation, producing light.

36 MATERIALS SCIENCE↗

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth and structural transitions of core-shell nanorods in nanocrystalline Al-Ni-Y

Unique nanorod precipitates with a core-shell structure are found to nucleate from the grain boundaries of a bulk nanocrystalline Al-Ni-Y alloy fabricated via powder consolidation, contributing significantly to stabilization and strengthening. The local structure, chemistry, and evolution of these features during annealing are reported here. In the as-consolidated state, the nanorods can be either structurally ordered or disordered, yet a consistent chemical patterning is found where the core is primarily Al plus C while the shell is enriched with Y. As annealing time increases, more nanorods transform to an ordered structure as they coarsen while the core composition remains unchanged. In contrast, the shell chemistry transitions from Y-rich to Ni-rich with longer annealing treatments, most likely due to the different diffusivities of Y and Ni in Al. Furthermore, a spatial and chemical correlation between the nanorods and amorphous complexions is observed, suggesting that these complexions serve as preferential nucleation sites.

36 MATERIALS SCIENCE↗

Near field excited state imaging via stimulated electron energy gain spectroscopy of localized surface plasmon resonances in plasmonic nanorod antennas

Continuous wave (cw) photon stimulated electron energy loss and gain spectroscopy (sEELS and sEEGS) is used to image the near field of optically stimulated localized surface plasmon resonance (LSPR) modes in nanorod antennas. An optical delivery system equipped with a nanomanipulator and a fiber-coupled laser diode is used to simultaneously irradiate plasmonic nanostructures in a (scanning) transmission electron microscope. The nanorod length is varied such that the m = 1, 2, and 3 LSPR modes are resonant with the laser energy and the optically stimulated near field spectra and images of these modes are measured. Various nanorod orientations are also investigated to explore retardation effects. Optical and electron beam simulations are used to rationalize the observed patterns. As expected, the odd modes are optically bright and result in observed sEEG responses. The m = 2 dark mode does not produce a sEEG response, however, when tilted such that retardation effects are operative, the sEEG signal emerges. Thus, we demonstrate that cw sEEGS is an effective tool in imaging the near field of the full set of nanorod plasmon modes of either parity.

36 MATERIALS SCIENCE↗

Nanorod-Based Fast-Response Pressure-Sensitive Paints

A proposed program of research and development would be devoted to exploitation of nanomaterials in pressuresensitive paints (PSPs), which are used on wind-tunnel models for mapping surface pressures associated with flow fields. Heretofore, some success has been achieved in measuring steady-state pressures by use of PSPs, but success in measuring temporally varying pressures has been elusive because of the inherent slowness of the optical responses of these materials. A PSP contains a dye that luminesces in a suitable wavelength range in response to photoexcitation in a shorter wavelength range. The luminescence is quenched by oxygen at a rate proportional to the partial pressure of oxygen and thus proportional to the pressure of air. As a result, the intensity of luminescence varies inversely with the pressure of air. The major problem in developing a PSP that could be easily applied to a wind-tunnel model and could be useful for measuring rapidly varying pressure is to provide very high gas diffusivity for rapid, easy transport of oxygen to and from active dye molecules. Most PSPs include polymer-base binders, which limit the penetration of oxygen to dye molecules, thereby reducing responses to pressure fluctuations. The proposed incorporation of nanomaterials (somewhat more specifically, nanorods) would result in paints having nanostructured surfaces that, relative to conventional PSP surfaces, would afford easier and more nearly complete access of oxygen molecules to dye molecules. One measure of greater access is effective surface area: For a typical PSP as proposed applied to a given solid surface, the nanometer-scale structural features would result in an exposed surface area more than 100 times that of a conventional PSP, and the mass of proposed PSP needed to cover the surface would be less than tenth of the mass of the conventional PSP. One aspect of the proposed development would be to synthesize nanorods of Si/SiO2, in both tangle-mat and regular- array forms, by use of chemical vapor deposition (CVD) and wet chemical processes, respectively. The rods would be coated with a PSP dye, and the resulting PSP signals would be compared with those obtained from PSP dye coats on conventional support materials. Another aspect of the proposed development would be to seek to exploit the quantum properties of nanorods of a suitable semiconductor (possibly GaN), which would be synthesized by CVD. These quantum properties of semiconductor nanorods include narrow-wavelength-band optical absorption and emission characteristics that vary with temperature. The temperature sensitivity might enable simultaneous measurement of fluctuating temperature and pressure and to provide a temperature correction for the PSP response.

Bencic, Timothy↗

Facet-Dependent Cold Welding of Au Nanorods Revealed by Liquid Cell Transmission Electron Microscopy

Cold welding of metals at the nanoscale has been demonstrated to play a significant role in bottom-up manufacturing and self-healing processes of nanostructures and nanodevices. However, the welding mechanism at the nanoscale is not well understood. In this study, a comprehensive demonstration of the cold welding process of gold nanorods with different modes is presented through in situ liquid cell transmission electron microscopy. The experimental results and molecular dynamics simulations reveal that the nanorods are welded through the facet-dependent atomic surface diffusion and rearrangement along {100} facets. The density functional theory calculations indicate that the preferred coalescence of two {100} surfaces is thermodynamically favorable. Unlike the prevalent “oriented attachment” in the nanoparticle coalescence, the misalignment of nanorod orientations and local stresses can induce grain boundaries and stacking faults in the welded interface.

42 ENGINEERING↗

In Situ Neutron Scattering Studies on the Oxidation and Reduction of CeO 2 and Pt–CeO 2 Nanorods

The oxygen vacancy structure of ceria plays a key role in its performance as a favored material for catalysis applications. Here, in this work, we develop an understanding of the effects of Pt loading on the structural evolution of ceria nanorods under redox gas environments that mimic real automotive catalytic converters. In situ neutron scattering studies under redox flow reveal that both CeO 2 and Pt–CeO 2 nanorods share a bulk fluorite structure with the presence of surface Frenkel-type oxygen defects. However, Pt–CeO 2 nanorods are more easily reducible than CeO 2 rods as evidenced by an increased concentration of Ce 3+ , determined by NAP-XPS. Importantly, this work finds no evidence of oxygen vacancy ordered surface reconstruction which has been reported in earlier ex situ investigations. Thus, this work highlights the discrepancy between ex situ and in situ structural observations and emphasizes the need for robust in situ investigations of catalysts to develop industrially relevant materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of a Picosecond Light-Induced Spin Transition in Polymeric Nanorods

Spin transition (ST) materials are attractive for developing photoswitchable devices, but their slow material transformations limit device applications. Size reduction could enable faster switching, but the photoinduced dynamics at the nanoscale remains poorly understood. Here, we report a femtosecond optical pump multimodal X-ray probe study of polymeric nanorods. Simultaneously tracking the ST order parameter with X-ray emission spectroscopy and structure with X-ray diffraction, we observe photodoping of the low-spin–lattice within ~150 fs. Above a ~16% photodoping threshold, the transition to the high-spin phase occurs following an incubation period assigned to vibrational energy redistribution within the nanorods activating the molecular spin switching. Above ~60% photodoping, the incubation period disappears, and the transition completes within ~50 ps, preceded by the elastic nanorod expansion in response to the photodoping. These results support the feasibility of ST material-based GHz optical switching applications.

36 MATERIALS SCIENCE↗

Emergence of a Low-Energy Peak in the Smoothed Absolute Value Circular Dichroism Spectra of Small Helical Gold Nanorods

We calculate, using time-dependent density functional theory, absorption and circular dichroism (CD) spectra for a series of small helical gold nanorod structures with a width of 0.6 nm and length increasing from 0.7 nm for Au 24 to 1.9 nm for Au 56 . For a low-energy window, ranging from 1.7 to 4.1 eV, broadening the lines in the absorption spectra results in a low energy peak which previous studies have identified as the (localized) plasmon resonance. As expected, the absorption peak position of the plasmon resonance systematically redshifts as the length of the nanorod increases. However, trends in the CD and straightforwardly broadened CD spectra are more difficult to discern. We introduce the idea of an absolute value CD spectrum and show that broadening the lines results in a low energy peak that has not previously been reported. The peak position systematically redshifts as the length of the nanorod increases but over a significantly smaller range than that for the absorption spectrum.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Modeling Surface-Enhanced Raman Scattering of Au-Pyrazine and Au-Pyrazine-Au Nanorod Dimer Systems with the TD-DFTB Method

This study investigates Raman scattering from a pyrazine molecule adsorbed on gold nanorod surfaces using the time-dependent density functional tight-binding (TD-DFTB) method. We analyze surface enhanced Raman scattering (SERS) of the molecule for two configurations: one where the molecule is adsorbed on a single gold nanorod forming Au-pyrazine complex, and another where it forms a nano-junction Au-pyrazine-Au dimer system. These two configurations offer distinct chemical environments for the molecule and different local field enhancements, with the dimer systems generating enhanced hotspot regions at the junctions. We present results for nanojunction, Au-pyrazine-Au dimer structures, for variable nanogap sizes that lead to shift in the plasmon energy. The study identifies contributions to the SERS enhancements from chemical, electromagnetic, and resonance charge transfer mechanisms. Our results show that the chemical mechanism provides enhancement factors in the range of 10 2 –10 3 , while the electromagnetic enhancements are on the order of 10 3 –10 5 for monomer systems and 10 6 –10 8 for dimer structures. We present results for a nanorod with a length of 5.3 nm and a width of 0.52 nm, consisting of 121 gold atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanorod length-dependent photodriven H2 production in 1D CdS–Pt heterostructures

Colloidal quantum confined semiconductor-metal heterostructures are promising candidates for solar energy conversion because their light absorbing semiconductor and catalytic components can be independently tuned and optimized. Although the light-to-hydrogen efficiencies of such systems have shown interesting dependences on the morphologies of the semiconductor and metal domains, the mechanisms of such dependences are poorly understood. Here, we use Pt tipped 0D CdS quantum dots (with ∼4.6 nm diameter) and 1D CdS nanorods (of ∼13.8, 27.8, 66.6, and 88.9 nm average rod lengths) as a model system to study the distance-dependence of charge separation and charge recombination times and their impacts on photo-driven H2 production. The H2 generation quantum efficiency increases from 0.2% ± 0.0% in quantum dots to 28.9% ± 0.4% at a rod length of 28 nm and shows negligible changes at longer rod lengths. The half-life time of electron transfer from CdS to Pt increases monotonically with rod length, from 0.7 ± 0.1 in quantum dots to 170.2 ± 29.5 ps in the longest rods, corresponding to a slight decrease in electron transfer quantum efficiency from 92% to 81%. The amplitude-weighted average lifetime of charge recombination of the electron in Pt with the hole in CdS increases from 4.7 ± 0.4 µs in quantum dots to 149 ± 34 µs in 28 nm nanorods, and the lifetime does not increase further in longer rods, resembling the trend in the observed H2 generation quantum efficiency. Our result suggests that the competition of the charge recombination process with the hole removal by the sacrificial electron donor plays a dominant role in the observed nanorod length dependent overall light driven H2 generation quantum efficiency.

Chemistry↗

Strain-modulated helimagnetism and emergent magnetic phase diagrams in highly crystalline MnP nanorod films

Here, we explore strain-modulated helimagnetism in highly crystalline MnP nanorod films grown on Si(100) substrates using molecular beam epitaxy. The strained MnP film exhibits a paramagnetic to ferromagnetic (FM) phase transition at $T_C$ ~ 279 K, and the FM to helical phase transition at $T_N$ ~ 110 K. The value of $T_N$ is greater than $T_N$ ~ 47K for the MnP single crystal, indicating strong strain-modulated helimagnetic states in the MnP nanorod film. The presence of significant thermal hysteresis in the helical phase indicates the coexistence of competing magnetic interactions, leading to the first-order metamagnetic transition. Similar to its single-crystal counterpart, an anisotropic magnetic effect is observed in the MnP film, which is independently confirmed by magnetic hysteresis loop and radio-frequency transverse susceptibility (TS) measurements. The evolution of the screw to the cone and fan phases is precisely tracked from magnetization vs magnetic field/temperature measurements. The temperature dependence of the anisotropy fields, extracted from the TS spectra, yields further insight into the competing nature of the magnetic phases. Unfolding of the different helical phases at $\textit{T}$ < 120 K (~$T_N$) is analyzed by the temperature- and field-dependent magnetic entropy change. Based on these findings, the comprehensive magnetic phase diagrams of the MnP nanorod film are constructed for both the in-plane and out of plane magnetic field directions, revealing emergent strain/dimensionality-driven helical magnetic features that are absent in the magnetic phase diagram of the MnP single crystal.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Diamond-Like Carbon Nanorods and Fabrication Thereof

Novel sp. (sup 3) rich diamond-like carbon (DLC) nanorod films were fabricated by hot filament chemical vapor deposition technique. The results are indicative of a bottom-up self-assembly synthesis process, which results in a hierarchical structure that consists of microscale papillae comprising numerous nanorods. The papillae have diameters ranging from 2 to 4 microns and the nanorods have diameters in the 35-45 nanometer range. A growth mechanism based on the vapor liquid-solid mechanism is proposed that accounts for the morphological aspects in the micro- and nano-scales.

Varshney, Deepak↗

Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures

We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, k n A = n 2 (n – 1)/4k 2 A , with a biexciton lifetime (1/k 2 A ) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Yttrium-based Double Perovskite Nanorods for Electrocatalysis

In this work, we investigate the effect of chemical composition of double perovskite nanorods on their versatile electrocatalytic activity not only as supports for the oxidation of small organic molecules but also as catalysts for the oxygen evolution reaction. Specifically, Y 2 CoMnO 6 and Y 2 NiMnO 6 nanorods with average diameters of 300 nm were prepared by a two-step hydrothermal method, in which the individual effects of synthetic parameters, such as the pH, annealing temperature, and precursor ratios on both the composition and morphology, were systematically investigated. When used as supports for Pt nanoparticles, Y 2 CoMnO 6 /Pt catalysts exhibited an electrocatalytic activity for the methanol oxidation reaction, which is 2.1 and 1.3 times higher than that measured for commercial Pt/C and Y 2 NiMnO 6 /Pt. Similarly, the Co-based catalyst support material displayed an ethanol oxidation activity, which is 2.3 times higher than both Pt/C and Y 2 NiMnO 6 /Pt. This clear enhancement in the activity for Y 2 CoMnO 6 can largely be attributed to strong metal-support interactions, as evidenced by a downshift in the binding energy of the Pt 4f bands, measured by XPS, which is often correlated not only with a downshift in the d-band center but also to a decreased adsorption of poisoning adsorbates. Moreover, when used as catalysts for the oxygen evolution reaction, Y 2 CoMnO 6 displayed a much greater activity as compared with Y 2 NiMnO 6 . This behavior can largely be attributed not only to a preponderance of comparatively more favorable oxidation states and electronic configurations but also to the formation of an active layer on the surface of the Y 2 CoMnO 6 catalyst, which collectively give rise to improved performance metrics and greater stability as compared with both IrO 2 and Y 2 NiMnO 6 . Overall, these results highlight the importance of both the chemical composition and the electronic structure of double perovskites, especially when utilized in multi-functional roles as either supports or catalysts.

30 DIRECT ENERGY CONVERSION↗

Probing the optical properties and toxicological profile of zinc tungstate nanorods

Zinc tungstate is a semiconductor known for its favorable photocatalytic, photoluminescence, and scintillation properties, coupled with its relatively low cost, reduced toxicity, and high stability in biological and catalytic environments. In particular, zinc tungstate evinces scintillation properties, namely the ability to emit visible light upon absorption of energetic radiation such as x rays, which has led to applications not only as radiation detectors but also for biomedical applications involving the delivery of optical light to deep tissue, such as photodynamic therapy and optogenetics. Here, we report on the synthesis of zinc tungstate nanorods generated via an optimized but facile method, which allows for synthetic control over the aspect ratio of the as-synthesized anisotropic motifs via rational variation of the solution pH. Additionally, we investigate the effect of aspect ratio on their resulting photoluminescent and radioluminescent properties. We further demonstrate the potential of these zinc tungstate nanorods for biomedical applications, such as photodynamic therapy for cancer treatment, by analyzing their toxicological profile within cell lines and neurons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗