Extraordinary sensitivity of the electronic structure and properties of single-walled carbon nanotubes to molecular charge-transfer

Interaction of single-walled carbon nanotubes with electron donor and acceptor molecules causes significant changes in the electronic and Raman spectra, the relative proportion of the metallic species increasing on electron donation through molecular charge transfer, as also verified by electrical resistivity measurements.Comment: 15 pages, 5 figurre

Penetration of alkali atoms throughout graphene membrane: theoretical modeling

Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout graphene membrane grown on silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate rather low (about 0.8 eV) energy barrier for the formation of temporary defects in carbon layer required for the penetration of Li at high concentration of adatoms, higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100{\deg}C and impenetrability of graphene membrane for Rb and Cs. Differences between epitaxial and free standing graphene for the penetration of alkali ions are also discussed.Comment: 16 pages, 3 figure, accepted to Nanoscal

Binding of Nucleobases with Single-Walled Carbon Nanotubes

We have calculated the binding energy of various nucleobases (guanine (G), adenine (A), thymine (T) and cytosine (C)) with (5,5) single-walled carbon nanotubes (SWNTs) using ab-initio Hartre-Fock method (HF) together with force field calculations. The gas phase binding energies follow the sequence G $>$ A $>$ T $>$ C. We show that main contribution to binding energy comes from van-der Wall (vdW) interaction between nanotube and nucleobases. We compare these results with the interaction of nucleobases with graphene. We show that the binding energy of bases with SWNTs is much lower than the graphene but the sequence remains same. When we include the effect of solvation energy (Poisson-Boltzman (PB) solver at HF level), the binding energy follow the sequence G $>$ T $>$ A $>$ C $>$, which explains the experiment\cite{zheng} that oligonucleotides made of thymine bases are more effective in dispersing the SWNT in aqueous solution as compared to poly (A) and poly (C). We also demonstrate experimentally that there is differential binding affinity of nucleobases with the single-walled carbon nanotubes (SWNTs) by directly measuring the binding strength using isothermal titration (micro) calorimetry. The binding sequence of the nucleobases varies as thymine (T) $>$ adenine (A) $>$ cytosine (C), in agreement with our calculation.Comment: 7 pages, 6 figure

Functionalization and solubilization of BN nanotubes by interaction with Lewis bases

By interaction with a trialkylamine or trialkylphosphine, BN nanotubes can be dispersed in a hydrocarbon medium with retention of the nanotube structure

Graphene-based electrochemical supercapacitors

Graphenes prepared by three different methods have been investigated as electrode materials in electrochemical supercapacitors. The samples prepared by exfoliation of graphitic oxide and by the transformation of nanodiamond exhibit high specific capacitance in aq. H2SO4, the value reaching up to 117 F/g. By using an ionic liquid, the operating voltage has been extended to 3.5 V (instead of 1 V in the case of aq. H2SO4), the specific capacitance and energy density being 75 F/g and 31.9 Wh kg−1 respectively. This value of the energy density is one of the highest values reported to date. The performance characteristics of the graphenes which are directly related to the quality, in terms of the number of layers and the surface area, are superior to that of single-walled and multi-walled carbon nanotubes

Monolayer surface chemistry enables 2-colour single molecule localisation microscopy of adhesive ligands and adhesion proteins.

Nanofabricated and nanopatterned surfaces have revealed the sensitivity of cell adhesion to nanoscale variations in the spacing of adhesive ligands such as the tripeptide arginine-glycine-aspartic acid (RGD). To date, surface characterisation and cell adhesion are often examined in two separate experiments so that the localisation of ligands and adhesion proteins cannot be combined in the same image. Here we developed self-assembled monolayer chemistry for indium tin oxide (ITO) surfaces for single molecule localisation microscopy (SMLM). Cell adhesion and spreading were sensitive to average RGD spacing. At low average RGD spacing, a threshold exists of 0.8 RGD peptides per µm2 that tether cells to the substratum but this does not enable formation of focal adhesions. These findings suggest that cells can sense and engage single adhesive ligands but ligand clustering is required for cell spreading. Thus, our data reveal subtle differences in adhesion biology that may be obscured in ensemble measurements

Electrical properties of inorganic nanowire-polymer composites

Composites of nanowires of ZnO, RuO2 and Ag with polyaniline (PANI) as well as polypyrrole (PPy) have been prepared, for the first time, by an in-situ process, in order to investigate their electrical properties. Characterization by electron microscopy and IR spectroscopy indicates that there is considerable interaction between the oxide nanowires and the polymer. The room-temperature resistivity of the composites prepared in-situ varies in the 0.01-400 Ω cm range depending on the composition. While the resistivities of the PANI-ZnONW and PPy-ZnONW composites prepared by the in-situ process are generally higher than that of PANI/PPy, those of PANI-RuO2NW and PANI-AgNW are lower. Composites of ZnONW with polyaniline prepared by an ex-situ process exhibit a resistivity close to that of polyaniline

Graphene-Based Nanocomposites for Energy Storage

Since the first report of using micromechanical cleavage method to produce graphene sheets in 2004, graphene/graphene-based nanocomposites have attracted wide attention both for fundamental aspects as well as applications in advanced energy storage and conversion systems. In comparison to other materials, graphene-based nanostructured materials have unique 2D structure, high electronic mobility, exceptional electronic and thermal conductivities, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. Therefore, they are considered as attractive materials for hydrogen (H2) storage and high-performance electrochemical energy storage devices, such as supercapacitors, rechargeable lithium (Li)-ion batteries, Li–sulfur batteries, Li–air batteries, sodium (Na)-ion batteries, Na–air batteries, zinc (Zn)–air batteries, and vanadium redox flow batteries (VRFB), etc., as they can improve the efficiency, capacity, gravimetric energy/power densities, and cycle life of these energy storage devices. In this article, recent progress reported on the synthesis and fabrication of graphene nanocomposite materials for applications in these aforementioned various energy storage systems is reviewed. Importantly, the prospects and future challenges in both scalable manufacturing and more energy storage-related applications are discussed

Ionic liquids at electrified interfaces

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules

Dielectric function and plasmonic behavior of Ga(II) and Ga(III)

In order to exploit gallium´s (Ga) rich polymorphism in the design of phase-change plasmonic systems, accurate understanding of the dielectric function of the different Ga-phases is crucial. The dielectric dispersion profiles of those phases appearing at atmospheric pressure have been reported in the literature, but there is no information on the dielectric function of the high-pressure Ga-phases. Through first principles calculations we present a comprehensive analysis of the interdependence of the crystal structure, band structure, and dielectric function of two high-pressure Ga phases (Ga(II) and Ga(III)). The plasmonic behavior of these high-pressure Ga-phases is compared to those stable (liquid- and α-Ga) and metastable (β-, γ- and δ-Ga) at atmospherics pressure. This analysis can have important implications in the design of pressure-driven phase-change Ga plasmonic devices and high-pressure SERS substrates.Y.G. and F.M. acknowledges the support by the Army Research Laboratory under Cooperative Agreement Number W911NF-17-2-0023 and by SODERCAN (Sociedad para el Desarrollo de Cantabria) and the Research Vicerrectorate of the University of Cantabria through project 4JU2864661. Y.G. thanks the University of Cantabria for her FPU grant. P.G.-F. and J.J. acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through grant number PGC2018-096955-B-C41