Metal oxide nanostructures by a simple hot water treatment.
ABSTRACT: Surfaces with metal oxide nanostructures have gained considerable interest in applications such as sensors, detectors, energy harvesting cells, and batteries. However, conventional fabrication techniques suffer from challenges that hinder wide and effective applications of such surfaces. Most of the metal oxide nanostructure synthesis methods are costly, complicated, non-scalable, environmentally hazardous, or applicable to only certain few materials. Therefore, it is crucial to develop a simple metal oxide nanostructure fabrication method that can overcome all these limitations and pave the way to the industrial application of such surfaces. Here, we demonstrate that a wide variety of metals can form metal oxide nanostructures on their surfaces after simply interacting with hot water. This method, what we call hot water treatment, offers the ability to grow metal oxide nanostructures on most of the metals in the periodic table, their compounds, or alloys by a one-step, scalable, low-cost, and eco-friendly process. In addition, our findings reveal that a "plugging" mechanism along with surface diffusion is critical in the formation of such nanostructures. This work is believed to be of importance especially for researchers working on the growth of metal oxide nanostructures and their application in functional devices.
Project description:The stable deposition of reactive nanostructures on metal electrodes is a key process for modern technologies including energy conversion/ storage, electrocatalysis or sensing. Here a facile, scalable route is reported, which allows the bulk nanostructuring of copper foam electrodes with metal, metal oxide or metal hydroxide nanostructures. A concentration-gradient driven synthetic approach enables the fabrication of Janus-type electrodes where one face features Cu(OH)2 nanowires, while the other face features CuO nanoflowers. Thermal or chemical conversion of the nanostructured surfaces into copper oxide or copper metal is possible whilst retaining the respective nanostructure morphologies. As proof of concept, the functionalized electrodes are promising in electrocatalytic water oxidation and water reduction reactions.
Project description:The fabrication, by an all electrochemical process, of porous Si/ZnO nanostructures with engineered structural defects, leading to strong and broadband deep level emission from ZnO, is presented. Such nanostructures are fabricated by a combination of metal-assisted chemical etching of Si and direct current electrodeposition of ZnO. It makes the whole fabrication process low-cost, compatible with Complementary Metal-Oxide Semiconductor technology, scalable and easily industrialised. The photoluminescence spectra of the porous Si/ZnO nanostructures reveal a correlation between the lineshape, as well as the strength of the emission, with the morphology of the underlying porous Si, that control the induced defects in the ZnO. Appropriate fabrication conditions of the porous Si lead to exceptionally bright Gaussian-type emission that covers almost the entire visible spectrum, indicating that porous Si/ZnO nanostructures could be a cornerstone material towards white-light-emitting devices.
Project description:Three-dimensional (3D) nanostructures combine properties of nanoscale materials with the advantages of being macro-sized pieces when the time comes to manipulate, measure their properties or make a device. However, the amount of compounds with the ability to self-organize in ordered 3D nanostructures is limited. Therefore, template-based fabrication strategies become the key approach towards 3D nanostructures. Here we report the simple fabrication of a template based on anodic aluminium oxide, having a well-defined, ordered, tunable, homogeneous 3D nanotubular network in the sub 100-nm range. The 3D templates are then employed to achieve 3D, ordered nanowire networks in Bi2Te3 and polystyrene. Finally, we demonstrate the photonic crystal behaviour of both the template and the polystyrene 3D nanostructure. Our approach may establish the foundations for future high-throughput, cheap, photonic materials and devices made of simple commodity plastics, metals and semiconductors.
Project description:Key chemical transformations require metal and redox sites in proximity at interfaces; however, in traditional oxide-supported materials, this requirement is met only at the perimeters of metal nanoparticles. We report that galvanic replacement can produce inverse FeOx/metal nanostructures in which the concentration of oxide species adjoining metal domains is maximal. The synthesis involves reductive deposition of rhodium or platinum and oxidation of Fe2+ from magnetite (Fe3O4). We discovered a parallel dissolution and adsorption of Fe2+ onto the metal, yielding inverse FeOx-coated metal nanoparticles. This nanostructure exhibits the intrinsic activity in selective CO2 reduction that simple metal nanoparticles have only at interfaces with the support. By enabling a simple way to control the surface functionality of metal particles, our approach is not only scalable but also enables a versatile palette for catalyst design.
Project description:Hollow nanostructures based on transition metal oxides (TMOs) with high surface-to-volumetric ratio, low density, and high loading capacity have received great attention for energy-related applications. However, the controllable fabrication of hybrid TMO-based hollow nanostructures in a simple and scalable manner remains challenging. Herein, a simple and scalable strategy is used to prepare hierarchical carbon nanofiber (CNF)-based bubble-nanofiber-structured and reduced graphene oxide (RGO)-based bubble-nanosheet-structured Co3O4 hollow supraparticle (HSP) composites (denoted as CNF/HSP-Co3O4 and RGO/HSP-Co3O4, respectively) by solution self-assembly of ultrasmall Co3O4 nanoparticles (NPs) assisting with polydopamine (PDA) modification. It is proved that the electrochemical performance of Co3O4 NPs can be greatly enhanced by the rationally designed nanostructure of bubble-like supraparticles combined with carbon materials as excellent electrodes for supercapacitors. The favorable structure and composition endow the hybrid electrode with high specific capacitance (1435 F g-1/1360 F g-1 at 1 A g-1/5 mV s-1) as well as fantastic rate capability. The asymmetric supercapacitors achieve an excellent maximum energy density of 51 W h kg-1 and superb electrochemical stability (92.3% retention after 10 000 cycles). This work suggests that the rational design of electrode materials with bubble-like superstructures provides an opportunity for achieving high-performance electrode materials for advanced energy storage devices.
Project description:Nanostructured potassium-incorporated Ti-based oxides have attracted much attention because the incorporated potassium can influence their structural and physico-chemical properties. With the aim of tuning the structural and physical properties, we have demonstrated the wet corrosion process (WCP) as a simple method for nanostructure fabrication using various Ti-based materials, namely Ti-6Al-4V alloy (TAV), Ti-Ni (TN) alloy and pure Ti, which have 90%, 50% and 100% initial Ti content, respectively. We have systematically investigated the relationship between the Ti content in the initial metal and the precise condition of WCP to control the structural and physical properties of the resulting nanostructures. The WCP treatment involved various concentrations of KOH solutions. The precise conditions for producing K-incorporated nanostructured titanium oxide films (nTOFs) were strongly dependent on the Ti content of the initial metal. Ti and TAV yielded one-dimensional nanowires of K-incorporated nTOFs after treatment with 10 mol/L-KOH solution, whereas TN required a higher concentration (20 mol/L-KOH solution) to produce comparable nanostructures. The obtained nanostructures revealed a blue-shift in UV absorption spectra due to the quantum confinement effects. A significant enhancement of the photocatalytic activity was observed via the chromomeric change and the intermediate formation of methylene blue molecules under UV irradiation. This study demonstrates the WCP as a simple, versatile and scalable method for the production of nanostructured K-incorporated nTOFs to be used as high-performance photocatalysts for environmental and energy applications.
Project description:In this work, two copper-based biometamaterials were engineered using leaves of water cabbage (Pistia stratiotes) and purple bauhinia (Phanera purpurea) as templates. The copper sputtering was implemented to produce a thin copper film on the surface of leaves. The scanning electron microscopy (SEM) images exhibited the root hair-like nanostructure of water cabbage leaf and single comb-like nanostructure of purple bauhinia leaf. In spite of copper coating, the leaf surfaces of water cabbage and purple bauhinia were black and exhibited excellent light absorption at visible and near infrarrred wavelengths. It was estimated that these two types of leaves could absorb roughly 90% of light. Finite-difference time-domain (FDTD) calculations predicted the low reflectance stemming from the leaf nanostructures and copper coating layer. Because of the low cost of copper as a coating metal and simple procedure, this can be a promising method for quick fabrication of a thin copper film on the leaf nanostructure for application in blackbody or as the light absorbers.
Project description:We propose two approaches-hot-embossing and dielectric-heating nanoimprinting methods-for low-cost and rapid fabrication of periodic nanostructures. Each nanofabrication process for the imprinted plastic nanostructures is completed within several seconds without the use of release agents and epoxy. Low-cost, large-area, and highly sensitive aluminum nanostructures on A4 size plastic films are fabricated by evaporating aluminum film on hot-embossing nanostructures. The narrowest bandwidth of the Fano resonance is only 2.7 nm in the visible light region. The periodic aluminum nanostructure achieves a figure of merit of 150, and an intensity sensitivity of 29,345%/RIU (refractive index unit). The rapid fabrication is also achieved by using radio-frequency (RF) sensitive plastic films and a commercial RF welding machine. The dielectric-heating, using RF power, takes advantage of the rapid heating/cooling process and lower electric power consumption. The fabricated capped aluminum nanoslit array has a 5 nm Fano linewidth and 490.46 nm/RIU wavelength sensitivity. The biosensing capabilities of the metallic nanostructures are further verified by measuring antigen-antibody interactions using bovine serum albumin (BSA) and anti-BSA. These rapid and high-throughput fabrication methods can benefit low-cost, highly sensitive biosensors and other sensing applications.
Project description:The large area scalable fabrication of supported porous metal and metal oxide nanomaterials is acknowledged as one of the greatest challenges for their eventual implementation in on-device applications. In this work, we will present a comprehensive revision and the latest results regarding the pioneering use of commercially available metal phthalocyanines and porphyrins as solid precursors for the plasma-assisted deposition of porous metal and metal oxide films and three-dimensional nanostructures (hierarchical nanowires and nanotubes). The most advanced features of this method relay on its ample general character from the point of view of the porous material composition and microstructure, mild deposition and processing temperature and energy constrictions and, finally, its straightforward compatibility with the direct deposition of the porous nanomaterials on processable substrates and device-architectures. Thus, taking advantage of the variety in the composition of commercially available metal porphyrins and phthalocyanines, we present the development of metal and metal oxides layers including Pt, CuO, Fe2O3, TiO2, and ZnO with morphologies ranging from nanoparticles to nanocolumnar films. In addition, we combine this method with the fabrication by low-pressure vapor transport of single-crystalline organic nanowires for the formation of hierarchical hybrid organic@metal/metal-oxide and @metal/metal-oxide nanotubes. We carry out a thorough characterization of the films and nanowires using SEM, TEM, FIB 3D, and electron tomography. The latest two techniques are revealed as critical for the elucidation of the inner porosity of the layers.
Project description:Controlled assembly of nanoscale objects into superstructures is of tremendous interests. Many approaches have been developed to fabricate organic-nanoparticle superstructures. However, effective fabrication of inorganic-nanoparticle superstructures (such as nanoparticles linked by metals) remains a difficult challenge. Here we show a novel, general method to assemble metals and nanoparticles rationally into nanocomposite superstructures. Novel metal-nanoparticle superstructures are achieved by self-assembly of liquid metals and nanoparticles in immiscible liquids driven by reduction of free energy. Superstructures with various architectures, such as metal-core/nanoparticle-shell, nanocomposite-core/nanoparticle-shell, network of metal-linked core/shell nanostructures, and network of metal-linked nanoparticles, were successfully fabricated by simply tuning the volume ratio between nanoparticles and liquid metals. Our approach provides a simple, general way for fabrication of numerous metal-nanoparticle superstructures and enables a rational design of these novel superstructures with desired architectures for exciting applications.