Semiconductor-like Sensitivity in Metallic Ultrathin Gold Nanowire-Based Sensors

Due to the ease of modification of electronic structure upon analyte adsorption, semiconductors have been the preferred materials as chemical sensors. At reduced dimension, however, the sensitivity of semiconductor-based sensors deteriorates significantly due to passivation, and often by increased band gap caused by quantum confinement. Using first-principles density functional theory combined with Boltzmann transport calculations, we demonstrate semiconductor-like sensitivity toward chemical species in ultrathin gold nanowires (AuNWs). The sensing mechanism is governed by the modification of the electronic structure of the AuNW as well as scattering of the charge carriers by analyte adsorption. Most importantly, the sensitivity exhibits a linear relationship with the electron affinities of the respective analytes. Based on this relationship, we propose an empirical parameter, which can predict an analyte-specific sensitivity of a AuNW, rendering them as effective sensors for a wide range of chemical analytes

Synthesis of Hollow Nanotubes of Zn₂SiO₄ or SiO₂: Mechanistic Understanding and Uranium Adsorption Behavior

We report a facile synthesis of Zn₂SiO₄ nanotubes using a two-step process consisting of a wet-chemical synthesis of core–shell ZnO@SiO₂ nanorods followed by thermal annealing. While annealing in air leads to the formation of hollow Zn₂SiO₄, annealing under reducing atmosphere leads to the formation of SiO₂ nanotubes. We rationalize the formation of the silicate phase at temperatures much lower than the temperatures reported in the literature based on the porous nature of the silica shell on the ZnO nanorods. We present results from in situ transmission electron microscopy experiments to clearly show void nucleation at the interface between ZnO and the silica shell and the growth of the silicate phase by the Kirkendall effect. The porous nature of the silica shell is also responsible for the etching of the ZnO leading to the formation of silica nanotubes under reducing conditions. Both the hollow silica and silicate nanotubes exhibit good uranium sorption at different ranges of pH making them possible candidates for nuclear waste management

Mechanistic Understanding of Formation of Ultrathin Single-Crystalline Pt Nanowires

Engineering anisotropic nanostructures of isotropic FCC metals (Au, Pt, or Pd) requires a symmetry-breaking mechanism. In wet chemical synthesis methods, a judicious selection of capping agents can help achieve the desired morphology. However, understanding the mechanism of formation is challenging due to the complex chemical environment and the limitation of time resolution to investigate the fast reactions. Here, we present the formation mechanism of ultrathin single-crystalline Pt nanowires using detailed electron microscopy investigations. Various control experiments performed suggest that the binding of ligand to the Pt surface (primary vs secondary amine) plays a crucial role not only in dictating the morphology but also in controlling the nanowire growth direction. Further, a ligand-exchange mechanism is adopted to separate these as-synthesized Pt nanowire bundles into well-separated wires. This is found to be a crucial step in controlling the surface accessibility and hence improving the electrocatalytic activity of the nanowires

Templated Synthesis of SiO₂ Nanotubes for Lithium-Ion Battery Applications: An In Situ (Scanning) Transmission Electron Microscopy Study

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core–shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge–discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li+-ion batteries

Templated Synthesis of SiO₂ Nanotubes for Lithium-Ion Battery Applications: An In Situ (Scanning) Transmission Electron Microscopy Study

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core–shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge–discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li+-ion batteries

Manipulation of Optoelectronic Properties and Band Structure Engineering of Ultrathin Te Nanowires by Chemical Adsorption

Band structure engineering is a powerful technique both for the design of new semiconductor materials and for imparting new functionalities to existing ones. In this article, we present a novel and versatile technique to achieve this by surface adsorption on low dimensional systems. As a specific example, we demonstrate, through detailed experiments and ab initio simulations, the controlled modification of band structure in ultrathin Te nanowires due to NO₂ adsorption. Measurements of the temperature dependence of resistivity of single ultrathin Te nanowire field-effect transistor (FET) devices exposed to increasing amounts of NO₂ reveal a gradual transition from a semiconducting to a metallic state. Gradual quenching of vibrational Raman modes of Te with increasing concentration of NO₂ supports the appearance of a metallic state in NO₂ adsorbed Te. Ab initio simulations attribute these observations to the appearance of midgap states in NO₂ adsorbed Te nanowires. Our results provide fundamental insights into the effects of ambient on the electronic structures of low-dimensional materials and can be exploited for designing novel chemical sensors

High aspect-ratio germanium-tin alloy nanowires: potential as highly efficient Li-Ion battery anodes

Here, the fabrication of a high aspect ratio (>440) Ge1−xSnx nanowires with super-thin (≈9 nm) diameter, much below the Bohr radius, using a simple solvothermal-like growth method under supercritical toluene conditions at a reaction temperature of 440 °C is reported. Ge1−xSnx nanowires are grown with varying amounts of Sn in Ge lattice, between 3.1 to 10.2 at%. The growth of the Ge1−xSnx alloy nanowires is achieved without any additional catalysts, and directly on current collector substrates (titanium) for application as Li-ion battery anodes. The electrochemical performance of the binder-free Ge1−xSnx nanowires as an anode material for Li-ion batteries is investigated via galvanostatic cycling and detailed analysis of differential capacity plots. The dimensions of the nanowires, and the amount of Sn in Ge, are critical to achieving a high specific capacity and capacity retention. Ge1−xSnx nanowires with the highest aspect ratios and with the lowest Sn content (3.1 at%) demonstrate exceptional capacity retention of ≈90% and 86% from the 10th to the 100th and 150th cycles respectively, while maintaining a very high specific capacity value of 1176 and 1127 mAh g−1 after the 100 and 150 cycles respectively.</p

One-step grown carbonaceous germanium nanowires and their application as highly efficient lithium-ion battery anodes

Developing a simple, cheap, and scalable synthetic method for the fabrication of functional nanomaterials is crucial. Carbon-based nanowire nanocomposites could play a key role in integrating group IV semiconducting nanomaterials as anodes into Li-ion batteries. Here, we report a very simple, one-pot solvothermal-like growth of carbonaceous germanium (C-Ge) nanowires in a supercritical solvent. C-Ge nanowires are grown just by heating (380−490 °C) a commercially sourced Ge precursor, diphenylgermane (DPG), in supercritical toluene, without any external catalysts or surfactants. The self-seeded nanowires are highly crystalline and very thin, with an average diameter between 11 and 19 nm. The amorphous carbonaceous layer coating on Ge nanowires is formed from the polymerization and condensation of light carbon compounds generated from the decomposition of DPG during the growth process. These carbonaceous Ge nanowires demonstrate impressive electrochemical performance as an anode material for Li-ion batteries with high specific charge values (>1200 mAh g−1 after 500 cycles), greater than most of the previously reported for other “binder-free” Ge nanowire anode materials, and exceptionally stable capacity retention. The high specific charge values and impressively stable capacity are due to the unique morphology and composition of the nanowires

One-step grown carbonaceous germanium nanowires and their application as highly efficient lithium-ion battery anodes

Developing a simple, cheap, and scalable synthetic method for the fabrication of functional nanomaterials is crucial. Carbon-based nanowire nanocomposites could play a key role in integrating group IV semiconducting nanomaterials as anodes into Li-ion batteries. Here, we report a very simple, one-pot solvothermal-like growth of carbonaceous germanium (C-Ge) nanowires in a supercritical solvent. C-Ge nanowires are grown just by heating (380−490 °C) a commercially sourced Ge precursor, diphenylgermane (DPG), in supercritical toluene, without any external catalysts or surfactants. The self-seeded nanowires are highly crystalline and very thin, with an average diameter between 11 and 19 nm. The amorphous carbonaceous layer coating on Ge nanowires is formed from the polymerization and condensation of light carbon compounds generated from the decomposition of DPG during the growth process. These carbonaceous Ge nanowires demonstrate impressive electrochemical performance as an anode material for Li-ion batteries with high specific charge values (>1200 mAh g−1 after 500 cycles), greater than most of the previously reported for other “binder-free” Ge nanowire anode materials, and exceptionally stable capacity retention. The high specific charge values and impressively stable capacity are due to the unique morphology and composition of the nanowires

One-Step Grown Carbonaceous Germanium Nanowires and Their Application as Highly Efficient Lithium-Ion Battery Anodes

Developing a simple, cheap, and scalable synthetic method for the fabrication of functional nanomaterials is crucial. Carbon-based nanowire nanocomposites could play a key role in integrating group IV semiconducting nanomaterials as anodes into Li-ion batteries. Here, we report a very simple, one-pot solvothermal-like growth of carbonaceous germanium (C-Ge) nanowires in a supercritical solvent. C-Ge nanowires are grown just by heating (380–490 °C) a commercially sourced Ge precursor, diphenylgermane (DPG), in supercritical toluene, without any external catalysts or surfactants. The self-seeded nanowires are highly crystalline and very thin, with an average diameter between 11 and 19 nm. The amorphous carbonaceous layer coating on Ge nanowires is formed from the polymerization and condensation of light carbon compounds generated from the decomposition of DPG during the growth process. These carbonaceous Ge nanowires demonstrate impressive electrochemical performance as an anode material for Li-ion batteries with high specific charge values (>1200 mAh g–1 after 500 cycles), greater than most of the previously reported for other “binder-free” Ge nanowire anode materials, and exceptionally stable capacity retention. The high specific charge values and impressively stable capacity are due to the unique morphology and composition of the nanowires