Anisotropic Carbon Nanotube Structures with High Aspect Ratio Nanopores for Li-Ion Battery Anodes.

Technological advances in membrane technology, catalysis, and electrochemical energy storage require the fabrication of controlled pore structures at ever smaller length scales. It is therefore important to develop processes allowing for the fabrication of materials with controlled submicron porous structures. We propose a combination of colloidal lithography and chemical vapor deposition of carbon nanotubes to create continuous straight pores with diameters down to 100 nm in structures with thicknesses of more than 300 µm. These structures offer unique features, including continuous and parallel pores with aspect ratios in excess of 3000, a low pore tortuosity, good electrical conductivity, and electrochemical stability. We demonstrate that these structures can be used in Li-ion batteries by coating the carbon nanotubes with Si as an active anode material.

Honeycomb-shaped carbon nanotube supports for BiVO4 based solar water splitting.

Advances in the synthesis and assembly of nanomaterials offer a unique opportunity to purposefully design structures according to the requirements of the targeted applications. This paper shows a process to create robust 3D carbon nanotube (CNT) structures, which provide an electrically conductive support for nanoparticle coating. We describe a process to reliably fabricate robust honeycomb structures with walls made out of aligned CNTs. We present a design of experimental analysis of this fabrication process and discuss methods to coat these honeycombs with BiVO4 for solar fuel applications. The proposed honeycomb structure allows for an efficient transport of electrons through the electrode, as well as an enhanced light-electrode interaction. Finally, we demonstrate that the developed CNT electrodes can survive harsh BiVO4 synthesis conditions and can subsequently be used as photoelectrodes for solar water splitting.

Hydrothermal Coating of Patterned Carbon Nanotube Forest for Structured Lithium-Ion Battery Electrodes.

Controlling the arrangement and interface of nanoparticles is essential to achieve good transfer of charge, heat, or mechanical load. This is particularly challenging in systems requiring hybrid nanoparticle mixtures such as combinations of organic and inorganic materials. This work presents a process to coat vertically aligned carbon nanotube (CNT) forests with metal oxide nanoparticles using microwave-assisted hydrothermal synthesis. Hydrothermal processes normally damage delicate CNT forests, which is addressed here by a combination of lithographic patterning, transfer printing, and reduction of the synthesis time. This process is applied for the fabrication of structured Li-ion battery (LIB) electrodes where the aligned CNTs provide a straight electron transport path through the electrode and the hydrothermal coating process is used to coat the CNTs with conversion anode materials for LIBs. These nanoparticles are anchored on the surface of the CNTs and batteries fabricated following this process show a fourfold longer cyclability. Finally, this process is used to create thick electrodes (350 µm) with a gravimetric capacity of over 900 mAh g-1 .

High Aspect Ratio Nanostructures Kill Bacteria via Storage and Release of Mechanical Energy.

The threat of a global rise in the number of untreatable infections caused by antibiotic-resistant bacteria calls for the design and fabrication of a new generation of bactericidal materials. Here, we report a concept for the design of antibacterial surfaces, whereby cell death results from the ability of the nanofeatures to deflect when in contact with attaching cells. We show, using three-dimensional transmission electron microscopy, that the exceptionally high aspect ratio (100-3000) of vertically aligned carbon nanotubes (VACNTs) imparts extreme flexibility, which enhances the elastic energy storage in CNTs as they bend in contact with bacteria. Our experimental and theoretical analyses demonstrate that, for high aspect ratio structures, the bending energy stored in the CNTs is a substantial factor for the physical rupturing of both Gram-positive and Gram-negative bacteria. The highest bactericidal rates (99.3% for Pseudomonas aeruginosa and 84.9% for Staphylococcus aureus) were obtained by modifying the length of the VACNTs, allowing us to identify the optimal substratum properties to kill different types of bacteria efficiently. This work highlights that the bactericidal activity of high aspect ratio nanofeatures can outperform both natural bactericidal surfaces and other synthetic nanostructured multifunctional surfaces reported in previous studies. The present systems exhibit the highest bactericidal activity of a CNT-based substratum against a Gram-negative bacterium reported to date, suggesting the possibility of achieving close to 100% bacterial inactivation on VACNT-based substrata.

Continuous flow chemical vapour deposition of carbon nanotube sea urchins.

Hybrid structures consisting of functional materials enhanced by carbon nanotubes (CNTs) have potential for a variety of high impact applications, as shown by the impressive progress in sensing and mechanical applications enabled by CNT-enhanced materials. The hierarchical organisation of CNTs with other materials is key to the design of macroscale devices benefiting from the unique properties of individual CNTs, provided CNT density, morphology and binding with other materials are optimized. In this paper, we provide an analysis of a continuous aerosol process to create a hybrid hierarchical sea urchin structure with CNTs organized around a functional metal oxide core. We propose a new mechanism for the growth of these carbon nanotube sea urchins (CNTSU) and give new insight into their chemical composition. To corroborate the new mechanism, we examine the influence of CNT growth conditions on CNTSU morphology and demonstrate a new in-line characterisation technique to continuously monitor aerosol CNT growth during synthesis, which enables industrial-scale production optimization. Based upon the new formation mechanism we describe the first substrate-based chemical vapour deposition growth of CNTSUs which increases CNT length and improves G to D ratio, which also allows for the formation of CNTSU carpets with unique structures.

Silver-Assisted Synthesis of Gold Nanorods: the Relation between Silver Additive and Iodide Impurities.

Seed-mediated methods employing cetyltrimethylammonium bromide (CTAB) as a surfactant, and silver salts as additives, are the most common synthetic strategies for high-yield productions of quality Au nanorods. However, the mechanism of these reactions is not yet fully understood and, importantly, significant lab-to-lab reproducibility issues still affect these protocols. In this study, the direct correlation between the hidden content of iodide impurities in CTAB reagents, which can drastically differ from different suppliers or batches, and the optimal concentration of silver required to maximize the nanorods yield is demonstrated. As a result, high-quality nanorods are obtained at different iodide contents. These results are interpreted based on the different concentrations of CTAB and cetyltrimethylammonium iodide (CTAI) complexes with Ag+ and Au+ metal ions in the growth solution, and their different binding affinity and reduction potential on distinct crystallographic planes. Notably, the exhaustive conversion of CTAI-Au+ to CTAI-Ag+ appears to be the key condition for maximizing the nanorod yield.

The role of substrate wettability in nanoparticle transfer from wrinkled elastomers: fundamentals and application toward hierarchical patterning.

We report on the role of surface wettability during the printing transfer of nanoparticles from wrinkled surfaces onto flat substrates. As we demonstrate, this parameter dominates the transfer process. This effect can further be utilized to transfer colloidal particles in a structured fashion, if the substrates are patterned in wettability. The resulting colloidal arrangements are highly regular over macroscopic surface areas and display distinct pattern features in both the micrometer and nanoscale regime. We study the obtained structures and discuss the potential of this approach for creating hierarchical particle assemblies of high complexity. Our findings not only contribute to a better understanding of technologically relevant colloidal assembly processes, but also open new avenues for the realization of novel materials consisting of nanoparticles. In this regard, the presented structuring method is especially interesting for the design of optically functional surface coatings.