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Highly Conducting Spaced TiO2 Nanotubes Enable Defined Conformal Coating with Nanocrystalline Nb2O5 and High Performance Supercapacitor Applications

Establishing self-organized spacing between TiO2 nanotubes allows for highly conformal Nb2 O5 deposition that can be adjusted to optimized supercapacitive behavior.

Spaced TiO2 nanotube arrays allow for a high performance hierarchical supercapacitor structure

In this work, we describe the synthesis and electrochemical properties of nitridated hierarchical TiO2 nanotubes as an electrode for supercapacitors. The hierarchical TiO2 nanostructures are formed by a controlled layer-by-layer TiO2 nanoparticle decoration on self-organized spaced TiO2 nanotubes. These structures are then annealed in a NH3 atmosphere at elevated temperature to convert the material to a nitride structure – this drastically enhances their electron-transport properties. The areal capacitance of hierarchical structures can be tuned by changing the number of decorated TiO2 nanoparticle layers. The capacitance enhancement of the hierarchical structures reaches a maximum when the surface area through nanoparticle deposition is highest and the conductivity via nitridation is optimized.

TiO2 nanotubes with laterally spaced ordering enable optimized hierarchical structures with significantly enhanced photocatalytic H2 generation

In the present work we grow self-organized TiO2 nanotube arrays with a defined and controlled regular spacing between individual nanotubes. These defined intertube gaps allow one to build up hierarchical 1D-branched structures, conformally coated on the nanotube walls using a layer by layer nanoparticle TiO2 decoration of the individual tubes, i.e. having not only a high control over the TiO2 nanotube host structure but also on the harvesting layers. After optimizing the intertube spacing, we build host-guest arrays that show a drastically enhanced performance in photocatalytic H2 generation, compared to any arrangement of conventional TiO2 nanotubes or conventional TiO2 nanoparticle layers. We show this beneficial effect to be due to a combination of an increased large surface area (mainly provided by the nanoparticle layers) with a fast transport of the harvested charge within the passivated 1D nanotubes. We anticipate that this type of hierarchical structures based on TiO2 nanotubes with adjustable spacing will find even wider application, as they provide an unprecedented controllable combination of surface area and carrier transport.

TiO2 nanotubes with different spacing, Fe2O3 decoration and their evaluation for Li-ion battery application

In the present work, we report on the use of organized TiO2 nanotube (NT) layers with a regular intertube spacing for the growth of highly defined α-Fe2O3 nano-needles in the interspace. These α-Fe2O3 decorated TiO2 NTs are then explored for Li-ion battery applications and compared to classic close-packed (CP) NTs that are decorated with various amounts of nanoscale α-Fe2O3. We show that NTs with tube-to-tube spacing allow uniform decoration of individual NTs with regular arrangements of hematite nano-needles. The tube spacing also facilitates the electrolyte penetration as well as yielding better ion diffusion. While bare CP NTs show a higher capacitance of 71 μAh cm-2 compared to bare spaced NTs with a capacitance of 54 μAh cm-2, the hierarchical decoration with secondary metal oxide, α-Fe2O3, remarkably enhances the Li-ion battery performance. Namely, spaced NTs with α-Fe2O3 decoration have an areal capacitance of 477 μAh cm-2, i.e. they have nearly ∼8 times higher capacitance. However, the areal capacitance of CP NTs with α-Fe2O3 decoration saturates at 208 μAh cm-2, i.e. is limited to ∼3 times increase.

Spaced Titania Nanotube Arrays Allow the Construction of an Efficient N-Doped Hierarchical Structure for Visible-Light Harvesting

Abstract Regularly spaced TiO2 nanotubes were prepared by anodizing a titanium substrate in triethylene glycol electrolyte at elevated temperature. In comparison to conventional TiO2 nanotubes, spaced nanotubes possess an adjustable spacing between the individual nanotubes; this allows for controlled buildup of a hierarchical nanoparticle‐on‐nanotube structure. Here, we use this principle for layer‐by‐layer decoration of the tubes with TiO2 nanoparticles. The hierarchical structure after N doping and NH3 treatment at 450 °C shows a significant enhancement of visible‐light absorption, although it only carries a low doping concentration of nitrogen. For optimized N‐doped and particle‐decorated spaced TiO2 nanotubes, a considerable improvement in photocatalytic activity is obtained in comparison with conventional N‐doped TiO2 nanotubes or comparable N‐doped nanoparticle films. This is attributed to an enhanced visible‐light absorption through the N‐doped nanoparticle shell and a fast charge separation between the shell and the one‐dimensional nanotubular core.

Nanoporous AuPt and AuPtAg alloy co-catalysts formed by dewetting–dealloying on an ordered TiO2 nanotube surface lead to significantly enhanced photocatalytic H2 generation

Effective co-catalysts are of key importance for photocatalytic H2 generation from aqueous environments. An attractive co-catalyst candidate are AuPt (metastable) alloys due to the synergistic electronic and chemical interaction of the constituents in the charge transfer and H2 evolution process. Here we introduce the fabrication of AuPt alloy nanoparticles with nanoporosity (pore size of 2-5 nm) fabricated on spaced TiO2 nanotubes. By dewetting a layered AgAuPt coating, we form AuPtAg alloy nanoparticles. From these alloys, Ag can selectively be dissolved leading to the desired nanoporous AuPt alloy particles with diameter in the range of 10-70 nm deposited as a gradient on the TiO2 nanotubes. A significant enhancement of photocatalytic H2 generation is obtained compared to the same loading of monometallic or nonporous alloy. The nanoporous AuPt particles provide not only a large surface area to volume ratio (and are thus more effective) but also show the intrinsic synergy of a AuPt alloy for H2 generation.

Spaced TiO2 Nanotubes Enable Optimized Pt Atomic Layer Deposition for Efficient Photocatalytic H2 Generation

Abstract In the present work, we report the use of TiO2 nanotube (NT) layers with a regular intertube spacing that are decorated by Pt nanoparticles through the atomic layer deposition (ALD) of Pt. These Pt‐decorated spaced (SP) TiO2 NTs are subsequently explored for photocatalytic H2 evolution and are compared to classical close‐packed (CP) TiO2 NTs that are also decorated with various amounts of Pt by using ALD. On both tube types, by varying the number of ALD cycles, Pt nanoparticles of different sizes and areal densities are formed, uniformly decorating the inner and outer walls from tube top to tube bottom. The photocatalytic activity for H2 evolution strongly depends on the size and density of Pt nanoparticles, driven by the number of ALD cycles. We show that, for SP NTs, a much higher photocatalytic performance can be achieved with significantly smaller Pt nanoparticles (i.e. for fewer ALD cycles) compared to CP NTs.