Single-Walled TiO2 Nanotubes: Enhanced Carrier-Transport Properties by TiCl4 Treatment.

In the present work we report significant enhancement of the photoelectrochemical properties of self- organized TiO2 nanotubes by a combined "de-coring" of classic nanotubes followed by an appropiate TiCl4 treatment. We show that, except for the expected particle decoration, a key effect of the TiCl4 treatment is that the electron transport characteristics in TiO2 nanotubes can be drastically improved, for example, we observe an enhancement of up to 70 % in electron-transport times.

Ultrafast growth of highly ordered anodic TiO2 nanotubes in lactic acid electrolytes.

In the present work, we show that fully functional self-organized TiO(2) nanotube layers can be electrochemically grown with an unprecedented growth rate if lactic acid (LA) is used as an additive during anodization. The main effect of LA addition is that it allows performing nanotube growth at significantly higher anodization voltage than in the LA free case, and this without dielectric oxide breakdown ("burning"). As a result, for example, 15 µm tube thick nanotube layers, suitable for a use in dye-sensitized solar cells (DSSCs) can be grown in 45 s and 7 µm tubes suitable for water splitting can be grown in 25 s.

Dye-sensitized TiO2 nanotube membranes act as a visible-light switchable diffusion gate.

Here we report that both-end open anodic TiO2 nanotube membranes, after sensitization with a Ru(ii)-based dye, exhibit visible-light switching properties for flow-through the nanotube channels. Under illumination, the gate is in an open state providing ∼four-times faster permeation of small molecules through the membrane compared to a dark state. Switching is reversible with no apparent dye degradation being observed. Gating is possible not only of permeating dye molecules but also of nanoprobes such as polystyrene nanospheres. Supported by quantitative modelling, we attribute the switching mechanism to light-induced changes of the charge distribution at the dye/TiO2 interface which in turn alters the hydrodynamics within the anodic tube membranes. This demonstrates that these simple dye-sensitized nanotube membranes can be used as an optically addressable flow-through gate in nanofluidics.

Synthesis of free-standing Ta3N5 nanotube membranes and flow-through visible light photocatalytic applications.

We report on free-standing Ta3N5 nanotubular membranes with open top and bottom, used as visible-light-active, flow-through photocatalytic micro-reactors. We grow first a robust anodic Ta2O5 layer, lift-off a membrane and convert to Ta3N5. Such membranes can easily, in a flow-through mode, degrade methylene blue under visible light (wavelength >400 nm) or solar illumination.

Fabrication of PEDOT Nanocone Arrays with Electrochemically Modulated Broadband Antireflective Properties.

Ordered nanocone arrays of the electroactive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) were fabricated by the simultaneous oxygen plasma etching of an electrodeposited PEDOT thin film coated with a hexagonally closed packed polystyrene bead monolayer. PEDOT nanocone arrays with an intercone spacing of 200 nm and an average nanocone height of 350 nm exhibited a low broadband reflectivity of <1.5% from 550 to 800 nm. Electrochemical modulation of the oxidation state of the PEDOT nanocone array film was used to change both its ex situ absorption spectrum (electrochromism) and reflection spectrum (electroreflectivity). The sign of the PEDOT nanocone array electroreflectivity was opposite to that observed from unmodified PEDOT thin films; this significant difference is attributed to the unique optical behavior of nanostructured surfaces with an interfacial layer that contains a graded mix of air and highly absorptive nanocones. The combined electrochromic and electroreflective behavior of the antireflective PEDOT nanocone array films should find promising applications in solar energy cells, sensors and other optical devices.

Aligned metal oxide nanotube arrays: key-aspects of anodic TiO2 nanotube formation and properties.

Over the past ten years, self-aligned TiO2 nanotubes have attracted tremendous scientific and technological interest due to their anticipated impact on energy conversion, environment remediation and biocompatibility. In the present manuscript, we review fundamental principles that govern the self-organized initiation of anodic TiO2 nanotubes. We start with the fundamental question: why is self-organization taking place? We illustrate the inherent key mechanistic aspects that lead to tube growth in various different morphologies, such as ripple-walled tubes, smooth tubes, stacks and bamboo-type tubes, and importantly the formation of double-walled TiO2 nanotubes versus single-walled tubes, and the drastic difference in their physical and chemical properties. We show how both double- and single-walled tube layers can be detached from the metallic substrate and exploited for the preparation of robust self-standing membranes. Finally, we show how by selecting specific growth approaches to TiO2 nanotubes desired functional features can be significantly improved, e.g., enhanced electron mobility, intrinsic doping, or crystallization into pure anatase at high temperatures can be achieved. Finally, we briefly outline the impact of property, modifications and morphology on functional uses of self-organized nanotubes for most important applications.

NH3 treatment of TiO2 nanotubes: from N-doping to semimetallic conductivity.

In the present work we show that a suitable high temperature ammonia treatment allows for the conversion of single-walled TiO2 nanotube arrays not only to a N-doped photoactive anatase material (which is already well established), but even further into fully functional titanium nitride (TiN) tubular structures that exhibit semimetallic conductivity.

Efficient and stable panchromatic squaraine dyes for dye-sensitized solar cells.

A new series of stable, unsymmetrical squaraine near-IR sensitizers (JK-216 and JK-217), which are assembled using both thiophenyl pyrrolyl and indolium groups, exhibit a panchromatic light harvesting up to 780 nm. The JK-216 based cell exhibited a record efficiency of 6.29% for near-IR DSSCs. In addition, the JK-217 device showed an excellent stability under a light soaking test at 60 °C for 1000 h.