Praveen K. Sekhar

Titanium dioxide-supported non-precious metal oxygen reduction electrocatalyst

A new non-precious metal oxygen reduction catalyst was developed via heat treatment of in situ polymerized polyaniline onto TiO(2) particles in the presence of Fe species. The TiO(2) provides for improved performance relative to a carbon black-based catalyst and, at a high catalyst loading, allows for reducing the performance gap between non-precious-metal catalyst and Pt/C to ca. 20 mV in RDE testing.

Ionic liquid-mediated sol–gel coatings for capillary microextraction

Ionic liquid (IL)-mediated sol-gel hybrid organic-inorganic materials present enormous potential for effective use in analytical microextraction. This opportunity, however, has not yet been explored. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol-gel reactions. In this work, we developed a method that overcomes this hurdle and provides IL-mediated advanced sol-gel materials for capillary microextraction (CME). We examined two different ILs: (a) a phosphonium-based IL, trihexyltetradecylphosphonium tetrafluoroborate, and (b) a pyridinium-based ionic liquid, N-butyl-4-methylpyridinium tetrafluoroborate. These ILs were evaluated in conjunction with two types of hydroxy-terminated polymers: (a) two Si-OH terminated polymers (PDMS and BMPO), and (b) two C-OH terminated polymers (PEG and polyTHF) that differ in their sol-gel reactivity. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol-gel reactions. The IL-mediated sol-gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions in off-line CME-GC compared to analogous sol-gel coatings prepared without any IL in the sol solution. Contrary to this, the IL-mediated sol-gel coatings prepared with C-OH terminated polymers provided lower extraction efficiencies compared to their IL-free counterparts. These observations were explained by (a) lower sol-gel reactivity of C-OH groups in PEG and polyTHF compared to Si-OH groups in PDMS and in hydrolyzed alkoxysilane precursors and (b) extremely high viscosity of ionic liquids. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol-gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol-gel material to be able to provide the desired sorbent characteristics. Additionally, IL-mediated sol-gel PDMS coatings provided run-to-run RSD values of 4.2-5.0% and detection limits ranging from 3.2 ng/L to 17.4 ng/L. PDMS sol-gels prepared without ILs provided RSD values of 2.8-14.1%, and detection limits ranging from 4.9 ng/L to 487.0 ng/L.

Selective growth of silica nanowires in silicon catalysed by Pt thin film

Selective growth of amorphous silica nanowires on a silicon wafer deposited with Pt thin film is reported. The mechanism of nanowire growth has been established to follow the vapour liquid solid (VLS) model via the PtSi phase acting as the catalyst. Nanowires grow with diameters ranging from 50 to 500xa0nm. These bottom-up grown nanowires exhibit photoluminescence with a stable emission of blue light at 430xa0nm under excitation. The effect of varying the seed layer thickness (Pt film) from 2 to 100xa0nm has been studied. It is observed that, above 10xa0nm thickness, a continuous layer of Pt(2)Si re-solidifies on the surface, inhibiting the growth of nanowires. The selectivity to the Pt thickness has been exploited to create regions of nanowires connected to conducting silicide (Pt(2)Si) simultaneously in a single furnace treatment. This novel approach has opened the gateways for realizing hybrid interconnects in silicon for various nano-optical applications such as the localization of light, low-dimensional waveguides for functional microphotonics, scanning near-field microscopy, and nanoantennae.

Ion implantation based selective synthesis of silica nanowires on silicon wafers

A new method for selective growth of silica nanowires on silicon wafers is demonstrated by using ion implantation through a mask. Pd ions are implanted into Si (100) to form nanoclusters of Pd. The nanoclusters get activated and act as catalyst silicide seeds for nanowire growth, when heated in an open tube quartz furnace, using Ar as carrier gas. Silica nanowires grow selectively only on the implanted region. The vapor-liquid-solid model of nanowire formation is shown to be valid. This method facilitates controlled localized and directed bottom-up growth of silica nanowires and may enable applications such as in on-chip optoelectronics, biosensors, microantennae, and metallic nanotubes.

Selective growth of silica nanowires using an Au catalyst for optical recognition of interleukin-10

The vapor-liquid-solid (VLS) growth procedure has been extended for the selective growth of silica nanowires on SiO(2) layer by using Au as a catalyst. The nanowires were grown in an open tube furnace at 1100u2009°C for 60xa0min using Ar as a carrier gas. The average diameter of these bottom-up nucleated wires was found to be 200xa0nm. Transmission electron microscopy analysis indicates the amorphous nature of these nanoscale wires and suggests an Si-silica heterostructure. The localized silica nanowires have been used as an immunoassay template in the detection of interleukin-10 which is a lung cancer biomarker. Such a nanostructured platform offered a tenfold enhancement in the optical response, aiding the recognition of IL-10 in comparison to a bare silica substrate. The role of nanowires in the immunoassay was verified through the quenching behavior in the photoluminescence (PL) spectra. Two orders of reduction in PL intensity have been observed after completion of the immunoassay with significant quenching after executing every step of the protocol. The potential of this site-specific growth of silica nanowires on SiO(2) as a multi-modal biosensing platform has been discussed.

Optical emission from erbium-doped silica nanowires

Infrared optical emission from erbium-doped silica nanowires is shown to have property characteristic of the material nanostructure and to provide the basis for the fabrication of integrated photonic devices and biosensors. Silica nanowires of approximately 150 nm diameter were grown on a silicon wafer by metal-induced growth using a thin (20 nm) sputter-deposited palladium layer as a catalyst. The resulting wires were then ion implanted with 110 keV ErO− ions and annealed at 900u2009°C to optically activate the erbium. These wires exhibited photoluminescence emission at 1.54u2002μm, characteristic of the I415/2−I413/2 transition in erbium; however, comparison to similarly implanted fused silica layers revealed stronger thermal quenching and longer luminescence lifetimes in the nanowire samples. The former is attributed to an increase in defect-induced quenching partly due to the large surface-volume ratio of the nanowires, while the latter is attributed to a reduction in the optical density of states associated ...

Trace detection and discrimination of explosives using electrochemical potentiometric gas sensors

In this article, selective and sensitive detection of trace amounts of pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) is demonstrated. The screening system is based on a sampling/concentrator front end and electrochemical potentiometric gas sensors as the detector. Preferential hydrocarbon and nitrogen oxide(s) mixed potential sensors based on lanthanum strontium chromite and Pt electrodes with yttria stabilized zirconia (YSZ) solid electrolyte were used to capture the signature of the explosives. Quantitative measurements based on hydrocarbon and nitrogen oxide sensor responses indicated that the detector sensitivity scaled proportionally with the mass of the explosives (1-3 μg). Moreover, the results showed that PETN, TNT, and RDX samples could be discriminated from each other by calculating the ratio of nitrogen oxides to hydrocarbon integrated area under the peak. Further, the use of front-end technology to collect and concentrate the high explosive (HE) vapors make intrinsically low vapor pressure of the HE less of an obstacle for detection while ensuring higher sensitivity levels. In addition, the ability to use multiple sensors each tuned to basic chemical structures (e.g., nitro, amino, peroxide, and hydrocarbon groups) in HE materials will permit the construction of low-cost detector systems for screening a wide spectrum of explosives with lower false positives than present-day technologies.

Statistical Weight Kinetics Modeling and Estimation for Silica Nanowire Growth Catalyzed by Pd Thin Film

This work intends to understand and model the kinetic aspect or the change of substrate weight over time in the selective growth of silica nanowires (NWs) catalyzed through Pd thin film. Various adsorption-induced, diffusion-induced, or unified vapor-liquid-solid (VLS) growth models have been developed to describe the NW length varying with time. Since NW length has been difficult to be measured, substrate weight change is therefore used as an alternative in this study to investigate growth kinetics of NWs. We investigate six different weight kinetics models in predicting weight changes during growth. Model estimation and comparison are conducted using both maximum-likelihood estimation (MLE) and Bayesian approaches. Owing to the embedded kinetics information in the nonlinear growth models, the Bayesian hierarchical model is shown to be more desirable when process data is limited.

A New Low-Temperature Electrochemical Hydrocarbon and NOx Sensor

In this article, a new investigation on a low-temperature electrochemical hydrocarbon and NOx sensor is presented. Based on the mixed-potential-based sensing scheme, the sensor is constructed using platinum and metal oxide electrodes, along with an Yttria-Stabilized Zirconia (YSZ)/Strontium Titanate (SrTiO3) thin-film electrolyte. Unlike traditional mixed-potential sensors which operate at higher temperatures (>400 °C), this potentiometric sensor operates at 200 °C with dominant hydrocarbon (HC) and NOx response in the open-circuit and biased modes, respectively. The possible low-temperature operation of the sensor is speculated to be primarily due to the enhanced oxygen ion conductivity of the electrolyte, which may be attributed to the space charge effect, epitaxial strain, and atomic reconstruction at the interface of the YSZ/STO thin film. The response and recovery time for the NOx sensor are found to be 7 s and 8 s, respectively. The sensor exhibited stable response even after 120 days of testing, with an 11.4% decrease in HC response and a 3.3% decrease in NOx response.

Facile synthesis of vanadium oxide nanowires

AbstractA simple growth process is reported for the synthesis of vanadium (II) oxide nanowires with an average width of 65xa0nm and up to 5xa0μm in length for growth at 1000xa0°C for 3xa0h. The vanadium (II) oxide nanowires were grown on a gold-coated silicon substrate at ambient pressure using a single heat zone furnace with Ar as the carrier gas. nGold was utilized as a catalyst for the growth of the nanowires. The growth temperature and heating time were varied to observe the nanowire morphology. An increase in nanowire width was observed with an increase in the heating temperature. A ninefold increase in the number density of the nanowires was observed when the heating time was changed from 30xa0min to 3xa0h. This is the first time a simple growth process for producing VO nanowires at ambient pressure has been demonstrated. Such a scheme enables wider use of VO nanowires in critical applications such as energy storage, gas sensors, and optical devices.