Oomman K. Varghese

Titanium oxide nanotube arrays prepared by anodic oxidation

Titanium oxide nanotubes were fabricated by anodic oxidation of a pure titanium sheet in an aqueous solution containing 0.5 to 3.5 wt% hydrofluoric acid. These tubes are well aligned and organized into high-density uniform arrays. While the tops of the tubes are open, the bottoms of the tubes are closed, forming a barrier layer structure similar to that of porous alumina. The average tube diameter, ranging in size from 25 to 65 nm, was found to increase with increasing anodizing voltage, while the length of the tube was found independent of anodization time. A possible growth mechanism is presented.

Vertically aligned single crystal TiO2 nanowire arrays grown directly on transparent conducting oxide coated glass: synthesis details and applications.

Single-crystal one-dimensional (1D) semiconductor architectures are important in materials-based applications requiring a large surface area, morphological control, and superior charge transport. Titania has widespread utility in applications including photocatalysis, photochromism, photovoltaics, and gas sensors. While considerable efforts have focused on the preparation of 1D TiO2, no methods have been available to grow crystalline nanowire arrays directly onto transparent conducting oxide (TCO) substrates, greatly limiting the performance of TiO2 photoelectrochemical devices. Herein, we present a straightforward low temperature method to prepare single crystal rutile TiO2 nanowire arrays up to 5 microm long on TCO glass via a non-polar solvent/hydrophilic substrate interfacial reaction under mild hydrothermal conditions. The as-prepared densely packed nanowires grow vertically oriented from the TCO glass substrate along the (110) crystal plane with a preferred (001) orientation. In a dye sensitized solar cell, N719 dye, using TiO2 nanowire arrays 2-3 microm long we achieve an AM 1.5 photoconversion efficiency of 5.02%.

Toward Solar Fuels: Photocatalytic Conversion of Carbon Dioxide to Hydrocarbons

The past several decades have seen a significant rise in atmospheric carbon dioxide levels resulting from the combustion of hydrocarbon fuels. A solar energy based technology to recycle carbon dioxide into readily transportable hydrocarbon fuel (i.e., a solar fuel) would help reduce atmospheric CO2 levels and partly fulfill energy demands within the present hydrocarbon based fuel infrastructure. We review the present status of carbon dioxide conversion techniques, with particular attention to a recently developed photocatalytic process to convert carbon dioxide and water vapor into hydrocarbon fuels using sunlight.

High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels

Efficient solar conversion of carbon dioxide and water vapor to methane and other hydrocarbons is achieved using nitrogen-doped titania nanotube arrays, with a wall thickness low enough to facilitate effective carrier transfer to the adsorbing species, surface-loaded with nanodimensional islands of cocatalysts platinum and/or copper. All experiments are conducted in outdoor sunlight at University Park, PA. Intermediate reaction products, hydrogen and carbon monoxide, are also detected with their relative concentrations underlying hydrocarbon production rates and dependent upon the nature of the cocatalysts on the nanotube array surface. Using outdoor global AM 1.5 sunlight, 100 mW/cm(2), a hydrocarbon production rate of 111 ppm cm(-2) h(-1), or approximately 160 microL/(g h), is obtained when the nanotube array samples are loaded with both Cu and Pt nanoparticles. This rate of CO(2) to hydrocarbon production obtained under outdoor sunlight is at least 20 times higher than previous published reports, which were conducted under laboratory conditions using UV illumination.

Long vertically aligned titania nanotubes on transparent conducting oxide for highly efficient solar cells.

Dye-sensitized solar cells consist of a random network of titania nanoparticles that serve both as a high-surface-area support for dye molecules and as an electron-transporting medium. Despite achieving high power conversion efficiencies, their performance is limited by electron trapping in the nanoparticle film. Electron diffusion lengths can be increased by transporting charge through highly ordered nanostructures such as titania nanotube arrays. Although titania nanotube array films have been shown to enhance the efficiencies of both charge collection and light harvesting, it has not been possible to grow them on transparent conducting oxide glass with the lengths needed for high-efficiency device applications (tens of micrometres). Here, we report the fabrication of transparent titania nanotube array films on transparent conducting oxide glass with lengths between 0.3 and 33.0 microm using a novel electrochemistry approach. Dye-sensitized solar cells containing these arrays yielded a power conversion efficiency of 6.9%. The incident photon-to-current conversion efficiency ranged from 70 to 80% for wavelengths between 450 and 650 nm.

Highly-ordered TiO2 nanotube arrays up to 220 µm in length: use in water photoelectrolysis and dye-sensitized solar cells

The fabrication of highly-ordered TiO2 nanotube arrays up to 134 µm in length by anodization of Ti foil has recently been reported (Paulose et al 2006 J. Phys. Chem. B 110 16179). This work reports an extension of the fabrication technique to achieve TiO2 nanotube arrays up to 220 µm in length, with a length-to-outer diameter aspect ratio of ≈1400, as well as their initial application in dye-sensitized solar cells and hydrogen production by water photoelectrolysis. The highly-ordered TiO2 nanotube arrays are fabricated by potentiostatic anodization of Ti foil in fluoride ion containing baths in combination with non-aqueous organic polar electrolytes including N-methylformamide, dimethyl sulfoxide, formamide, or ethylene glycol. Depending upon the anodization voltage, the inner pore diameters of the resulting nanotube arrays range from 20 to 150 nm. As confirmed by glancing angle x-ray diffraction and HRTEM studies, the as-prepared nanotubes are amorphous but crystallize with annealing at elevated temperatures.

Crystallization and high-temperature structural stability of titanium oxide nanotube arrays

The stability of titanium oxide nanotube arrays at elevated temperatures was studied in dry oxygen as well as dry and humid argon environments. The tubes crystallized in the anatase phase at a temperature of about 280 °C irrespective of the ambient. Anatase crystallites formed inside the tube walls and transformed completely to rutile at about 620 °C in dry environments and 570 °C in humid argon. No discernible changes in the dimensions of the tubes were found when the heat treatment was performed in oxygen. However, variations of 10% and 20% in average inner diameter and wall thickness, respectively, were observed when annealing in a dry argon atmosphere at 580 °C for 3 h. Pore shrinkage was even more pronounced in humid argon environments. In all cases the nanotube architecture was found to be stable up to approximately 580 °C, above which oxidation and grain growth in the titanium support disrupted the overlying nanotube array.

Gas sensing characteristics of multi-wall carbon nanotubes

Abstract Impedance spectroscopy was used to study the gas sensing behavior of both capacitance and resistance based sensors employing multi-wall carbon nanotubes (MWNTs) as the active sensing element. Studies revealed the chemisorption of reducing gases upon the surface of the MWNTs. Increasing sensor impedance was observed with increasing humidity or partial pressures of ammonia, carbon monoxide, and carbon dioxide. The impedance changes are attributed to p-type conductivity in semiconducting MWNTs, and the formation of Schottky barriers between the metallic and semiconducting nanotubes. Reversible behavior is demonstrated for the MWNT sensors in response to humidity, carbon monoxide and carbon dioxide. The MWNT sensors strongly respond to ammonia behaving as dosimeters.

The Effect of Electrolyte Composition on the Fabrication of Self-Organized Titanium Oxide Nanotube Arrays by Anodic Oxidation

We report on the fabrication of self-organized titanium oxide nanotube arrays of enhanced surface area prepared by anodic oxidation of a pure titanium sheet in electrolyte solutions containing potassium fluoride (KF) or sodium fluoride (NaF). The effects of electrolyte composition and concentration, solution pH, and the anodic potential on the formation of nanotubes and dimensions of the resulting nanotubes are detailed. Although nanotube arrays of length greater than 500 nm are not possible with hydrofluoric acid containing electrolytes [G.K. Mor, O.K. Varghese, M. Paulose,N. Mukherjee, C.A. Grimes, J. Mater. Res . 18, 2588 (2003)], by adjusting the pH of a KF containing electrolyte to 4.5 using additives such as sulfuric acid, sodium hydroxide, sodium hydrogen sulfate, and/or citric acid, we could increase the length of the nanotube-array to approximately 4.4 μm, an order of magnitude increase in length. The as-prepared nanotubes are composed of amorphous titanium oxide. Independent of the electrolyte composition, crystallization of the nanotubes to anatase phase occurred at temperatures ⩾280 °C. Rutile formation occurred at the nanotube-Ti substrate interface at temperatures near 480 °C. It appears geometry constraints imposed by the nanotube walls inhibit anatase to rutile transformation. No disintegration of the nanotube array structure is observed at temperatures as high as 580 °C. The excellent structural and crystal phase stability of these nanotubes make them promising for both low- and high-temperature applications.

Fabrication of tapered, conical-shaped titania nanotubes

Using anodic oxidation with a time-dependent linearly varying anodization voltage, we have made films of tapered, conical-shaped titania nanotubes. The tapered, conical-shaped nanotubes were obtained by anodizing titanium foil in a 0.5% hydrofluoric acid electrolyte, with the anodization voltage linearly increased from 10-23 V at rates varying from 2.0-0.43 V/min. The linearly increasing anodization voltage results in a linearly increasing nanotube diameter, with the outcome being an array of conical-shaped nanotubes approximately 500 nm in length. Evidence provided by scanning electron-microscope images of the titanium substrate during the initial stages of the anodization process enabled us to propose a mechanism of nanotube formation.