Chandra Sekhar Tiwary

Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes.

The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (-0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed COOH and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.

Blue orange light emission from biogenic synthesized silver nanoparticles using Trichoderma viride

Recent advances in nanomaterial have produced a new class of fluorescence labels by conjugating noble metal with biomolecules. The nanometer size metal conjugates are water soluble, biocompatible and provide important advantage over the fluorescence dyes. In this regard we synthesized silver nanoparticles at the size of 2-4 nm using biological route and studied fluorescence property of these nanoparticles. We observe that these silver (Ag(+)) ions when exposed to filtrate of Trichoderma viride are reduced in solution, thereby leading to the formation of an extremely stable silver hydrosol. These silver nanoparticles were characterized by means of UV-vis spectrophotometer, FTIR, HrTEM, EDX, XRD and fluorescence spectroscopy. The nanoparticles exhibit maximum absorbance at 405 nm in UV-vis spectrum. The presence of proteins was identified by FTIR. The HrTEM micrograph revealed the formation of monodispersed spherical nanoparticles and the presence of elemental silver was confirmed by EDX analysis and XRD. These monodispersed silver nanoparticles showed emission in the range of 320-520 nm wavelength.

Nitrogen‐Doped Carbon Nanotube Arrays for High‐Efficiency Electrochemical Reduction of CO2: On the Understanding of Defects, Defect Density, and Selectivity

Nitrogen-doped carbon nanotubes (NCNTs) have been considered as a promising electrocatalyst for carbon-dioxide-reduction reactions, but two fundamental chemistry questions remain obscure: 1) What are the active centers with respect to various defect species and 2) what is the role of defect density on the selectivity of NCNTs? The aim of this work is to address these questions. The catalytic activity of NCNTs depends on the structural nature of nitrogen in CNTs and defect density. Comparing with pristine CNTs, the presence of graphitic and pyridinic nitrogen significantly decreases the overpotential (ca. -0.18 V) and increases the selectivity (ca. 80%) towards the formation of CO. The experimental results are in congruent with DFT calculations, which show that pyridinic defects retain a lone pair of electrons that are capable of binding CO2. However, for graphitic-like nitrogen, electrons are located in the π* antibonding orbital, making them less accessible for CO2 binding.

Chemical Vapor Deposition of Monolayer Rhenium Disulfide (ReS2)

The direct synthesis of monolayer and multilayer ReS2 by chemical vapor deposition at a low temperature of 450 °C is reported. Detailed characterization of this material is performed using various spectroscopy and microscopy methods. Furthermore initial field-effect transistor characteristics are evaluated, which highlight the potential in being used as an n-type semiconductor.

Low-density three-dimensional foam using self-reinforced hybrid two-dimensional atomic layers

Low-density nanostructured foams are often limited in applications due to their low mechanical and thermal stabilities. Here we report an approach of building the structural units of three-dimensional (3D) foams using hybrid two-dimensional (2D) atomic layers made of stacked graphene oxide layers reinforced with conformal hexagonal boron nitride (h-BN) platelets. The ultra-low density (1/400 times density of graphite) 3D porous structures are scalably synthesized using solution processing method. A layered 3D foam structure forms due to presence of h-BN and significant improvements in the mechanical properties are observed for the hybrid foam structures, over a range of temperatures, compared with pristine graphene oxide or reduced graphene oxide foams. It is found that domains of h-BN layers on the graphene oxide framework help to reinforce the 2D structural units, providing the observed improvement in mechanical integrity of the 3D foam structure.

Carbon Nitrogen Nanotubes as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions

Oxygen reduction and evolution reactions are essential for broad range of renewable energy technologies such as fuel cells, metal-air batteries and hydrogen production through water splitting, therefore, tremendous effort has been taken to develop excellent catalysts for these reactions. However, the development of cost-effective and efficient bifunctional catalysts for both reactions still remained a grand challenge. Herein, we report the electrocatalytic investigations of bamboo-shaped carbon nitrogen nanotubes (CNNTs) having different diameter distribution synthesized by liquid chemical vapor deposition technique using different nitrogen containing precursors. These CNNTs are found to be efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. The electrocatalytic activity strongly depends on the nanotube diameter as well as nitrogen functionality type. The higher diameter CNNTs are more favorable for these reactions. The increase in nanotube diameter itself enhances the catalytic activity by lowering the oxygen adsorption energy, better conductivity, and further facilitates the reaction by increasing the percentage of catalytically active nitrogen moieties in CNNTs.

Palladium Nanoparticles Supported on Nitrogen and Sulfur Dual-Doped Graphene as Highly Active Electrocatalysts for Formic Acid and Methanol Oxidation

Optimized designing of highly active electrocatalysts has been regarded as a critical point to the development of portable fuel cell systems with high power density. Here we report a facile and cost-effective strategy to synthesis of ultrafine Pd nanoparticles (NPs) supported on N and S dual-doped graphene (NS-G) nanosheets as multifunctional electrocatalysts for both direct formic acid fuel cell and direct methanol fuel cell. The incorporation of N and S atoms into graphene frameworks is achieved by a thermal treatment process, followed by the controlled growth of Pd NPs via a solvothermal approach. Owning to the unique structural features as well as the strong synergistic effects, the resulting Pd/NS-G hybrid exhibits outstanding electrocatalytic performance toward both formic acid and methanol electro-oxidation, such as higher anodic peak current densities and more exceptional catalytic stability than those of Pd/Vulcan XC-72R and Pd/undoped graphene catalysts. These findings open up new possibility in the construction of advanced Pd-based catalysts, which is conducive to solving the current bottlenecks of fuel cell technologies.

Nanodiamond-Based Thermal Fluids

Dispersions of nanodiamond (average size ∼6 nm) within dielectric insulator mineral oil are reported for their enhanced thermal conductivity properties and potential applications in thermal management. Dynamic and kinematic viscosities-very important parameters in thermal management by nanofluids-are investigated. The dependence of the dynamic viscosity is well-described by the theoretical predictions of Einsteins model. The temperature dependence of the dynamic viscosity obeys an Arrhenius-like behavior, where the activation energy and the pre-exponential factor have an exponential dependence on the filler fraction of nanodiamonds. An enhancement in thermal conductivity up to 70% is reported for nanodiamond based thermal fluids. Additional electron microscopy, Raman spectroscopy and X-ray diffraction analysis support the experimental data and their interpretation.

Enhanced field emission properties from CNT arrays synthesized on Inconel superalloy.

One of the most promising materials for fabricating cold cathodes for next generation high-performance flat panel devices is carbon nanotubes (CNTs). For this purpose, CNTs grown on metallic substrates are used to minimize contact resistance. In this report, we compare properties and field emission performance of CNTs grown via water assisted chemical vapor deposition using Inconel vs silicon (Si) substrates. Carbon nanotube forests grown on Inconel substrates are superior to the ones grown on silicon; low turn-on fields (∼1.5 V/μm), high current operation (∼100 mA/cm(2)) and very high local field amplification factors (up to ∼7300) were demonstrated, and these parameters are most beneficial for use in vacuum microelectronic applications.

Unzipping Carbon Nanotubes at High Impact

The way nanostructures behave and mechanically respond to high impact collision is a topic of intrigue. For anisotropic nanostructures, such as carbon nanotubes, this response will be complicated based on the impact geometry. Here we report the result of hypervelocity impact of nanotubes against solid targets and show that impact produces a large number of defects in the nanotubes, as well as rapid atom evaporation, leading to their unzipping along the nanotube axis. Fully atomistic reactive molecular dynamics simulations are used to gain further insights of the pathways and deformation and fracture mechanisms of nanotubes under high energy mechanical impact. Carbon nanotubes have been unzipped into graphene nanoribbons before using chemical treatments but here the instability of nanotubes against defect formation, fracture, and unzipping is revealed purely through mechanical impact.