Thomas J. LaTempa

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%.

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.

Highly Efficient Solar Cells using TiO2 Nanotube Arrays Sensitized with a Donor-Antenna Dye

Donor antenna dyes provide an exciting route to improving the efficiency of dye sensitized solar cells owing to their high molar extinction coefficients and the effective spatial separation of charges in the charge-separated state, which decelerates the recombination of photogenerated charges. Vertically oriented TiO(2) nanotube arrays provide an optimal material architecture for photoelectrochemical devices because of their large internal surface area, lower recombination losses, and vectorial charge transport along the nanotube axis. In this study, the results obtained by sensitizing TiO(2) nanotube arrays with the donor antenna dye Ru-TPA-NCS are presented. Solar cells fabricated using an antenna dye-sensitized array of 14.4 microm long TiO(2) nanotubes on Ti foil subjected to AM 1.5 one sun illumination in the backside geometry exhibited an overall conversion efficiency of 6.1%. An efficiency of 4.1% was obtained in the frontside illumination geometry using a 1 microm long array of transparent TiO(2) nanotubes subjected to a TiCl(4) treatment and then sensitized with the Ru-TPA-NCS dye. Open circuit voltage decay measurements give insight into the recombination behavior in antenna-dye sensitized nanotube photoelectrodes, demonstrating outstanding properties likely due to a reduction in the influence of the surface traps and reduced electron transfer from TiO(2) to ions in solution.

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation.

Copper and titanium remain relatively plentiful in the earths crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.

Long-Term Small Molecule and Protein Elution from TiO2 Nanotubes

In this study, TiO(2) nanotubes of various dimensions were used to elute albumin, a large protein molecule, as well as sirolimus and paclitaxel, common small molecule drugs. The nanotubes controlled small molecule diffusion for weeks and large molecule diffusion for a month. Drug eluted from the nanotubes was bioactive and decreased cell proliferation in vitro. Elution kinetics was most profoundly affected by tube height. This study demonstrates that TiO(2) nanotubes may be a promising candidate for a drug-eluting implant coating.

Ta3N5 Nanotube Arrays for Visible Light Water Photoelectrolysis

Tantalum nitride (Ta3N5) has a band gap of approximately 2.07 eV, suitable for collecting more than 45% of the incident solar spectrum energy. We describe a simple method for scale fabrication of highly oriented Ta3N5 nanotube array films, by anodization of tantalum foil to achieve vertically oriented tantalum oxide nanotube arrays followed by a 700 degrees C ammonia anneal for sample crystallization and nitridation. The thin walled amorphous nanotube array structure enables transformation from tantalum oxide to Ta3N5 to occur at relatively low temperatures, while high-temperature annealing related structural aggregation that commonly occurs in particle films is avoided. In 1 M KOH solution, under AM 1.5 illumination with 0.5 V dc bias typical sample (nanotube length approximately 240 nm, wall thickness approximately 7 nm) visible light incident photon conversion efficiencies (IPCE) as high as 5.3% were obtained. The enhanced visible light activity in combination with the ordered one-dimensional nanoarchitecture makes Ta3N5 nanotube arrays films a promising candidate for visible light water photoelectrolysis.

Synthesis and deposition of ultrafine Pt nanoparticles within high aspect ratio TiO2 nanotube arrays: application to the photocatalytic reduction of carbon dioxide

Using a rapid microwave-assisted solvothermal approach ultrafine Pt nanoparticles are synthesized and deposited in situ within high aspect ratio nanotube arrays. Adjusting the initial concentration of metal ion precursor inside the nanotube support controls the resulting Pt nanoparticle sizes. The Pt-nanoparticle/TiO2 nanotube composite is shown to greatly promote the photocatalytic conversion of carbon dioxide and water vapor into methane, a behavior attributed to the homogeneous distribution of metal co-catalyst nanoparticles over the TiO2 nanotube array surface providing a large number of active reduction sites. The novelty and flexibility of the technique, described herein, could prove useful for the deposition of metal, metal alloy, or metal oxide nanoparticles within a variety of nanotubular or nanoporous material systems with the resulting nanocomposites useful in catalysis, photocatalysis, photovoltaic, and photoelectrochemical applications.

Whole Genome Expression Analysis Reveals Differential Effects of TiO2 Nanotubes on Vascular Cells

The response of primary human endothelial (ECs) and vascular smooth muscle cells (VSMCs) to TiO2 nanotube arrays is studied through gene expression analysis. Microarrays revealed that nanotubes enhanced EC proliferation and motility, decreased VSMC proliferation, and decreased expression of molecules involved in inflammation and coagulation in both cell types. Networks generated from significantly affected genes suggest that cells may be sensing nanotopographical cues via pathways previously implicated in sensing shear stress.

Ethanol vapor processing of titania nanotube array films: enhanced crystallization and photoelectrochemical performance

A significant enhancement in the photoconversion efficiency of anodically grown, thermally annealed titania nanotube array photoanodes was observed when subjected to an ethanol vapor treatment that resulted in improved crystallization. Ethanol vapor treatment of 6 µm long vertically aligned titania nanotube array films initially annealed at 580 °C for 6 h in an oxygen environment, under autogeneous pressure at 140 °C (≈50 psi), resulted in an increase of up to ∼30% in the photoconversion efficiency. A significant improvement in the crystallinity as revealed by glancing angle X-ray diffraction (GAXRD) and Raman spectroscopy studies as well as incident photon to current conversion efficiency (IPCE) is observed in the vapor treated samples.

The effects of cell density and device arrangement on the behavior of macroencapsulated beta-cells.

Over the last several decades, considerable research has focused on the development of cell encapsulation technology to treat a number of diseases, especially type 1 diabetes. One of the key advantages of cell encapsulation is that it permits the use of xenogenic tissue, particularly animal-derived cell lines. This is an attractive idea, because it circumvents the issue of a limited human organ supply. Furthermore, as opposed to whole islets, cell lines have a better proliferative capacity and can easily be amplified in culture to provide an endless supply of uniform cells. We have previously described a macroencapsulation device for the immunoisolation of insulin-secreting β-cells. The aim of this work was to optimize the viability and insulin secretion of cells encapsulated within this device. Specifically, the effects of cell packing density and device membrane configuration were investigated. The results indicated that cell density plays an important role in the secretory capacity of the cells, with higher cell density leading to increased insulin secretion. Increasing the transport area of the capsule by modifying the membrane configuration also led to an improvement in the insulin output of the device.