Selective and low temperature transition metal intercalation in layered tellurides

Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80?°C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid

Visualizing Graphene Based Sheets by Fluorescence Quenching Microscopy

Graphene based sheets have stimulated great interest due to their superior mechanical, electrical and thermal properties. A general visualization method that allows quick observation of these single atomic layers would be highly desirable as it can greatly facilitate sample evaluation and manipulation, and provide immediate feedback to improve synthesis and processing strategies. Here we report that graphene based sheets can be made highly visible under a fluorescence microscope by quenching the emission from a dye coating, which can be conveniently removed afterwards by rinsing without disrupting the sheets. Current imaging techniques for graphene based sheets rely on the use of special substrates. In contrast, the fluorescence quenching mechanism is no longer limited by the types of substrates. Graphene, reduced graphene oxide, or even graphene oxide sheets deposited on arbitrary substrates can now be readily visualized by eye with good contrast for layer counting. Direct observation of suspended sheets in solution was also demonstrated. The fluorescence quenching microscopy offers unprecedented imaging flexibility and could become a general tool for characterizing graphene based materials.Comment: J. Am. Chem. Soc., Article ASA

Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons.

Published versio

NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional 13C Solid-State NMR and ab Initio Chemical Shift Calculations

Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D C-13 double-quantum/single-quantum correlation SSNMR spectrum of C-13-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf-Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp(2), 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). C-13 chemical shift anisotropy (CSA) patterns measured by a 2D C-13 CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems

Modeling of graphite oxide

Based on density functional calculations, optimized structures of graphite oxide are found for various coverage by oxygen and hydroxyl groups, as well as their ratio corresponding to the minimum of total energy. The model proposed describes well known experimental results. In particular, it explains why it is so difficult to reduce the graphite oxide up to pure graphene. Evolution of the electronic structure of graphite oxide with the coverage change is investigated.Comment: 12 pages, 7 figures. Discussion about reduction to pure graphene and several references added. Methodological part expanded. Accepted to J. Am. Chem. So

Probing the Thermal Deoxygenation of Graphene Oxide using High Resolution In Situ X-Ray based Spectroscopies

Despite the recent developments in Graphene Oxide due to its importance as a host precursor of Graphene, the detailed electronic structure and its evolution during the thermal reduction remain largely unknown, hindering its potential applications. We show that a combination of high resolution in situ X-ray photoemission and X-ray absorption spectroscopies offer a powerful approach to monitor the deoxygenation process and comprehensively evaluate the electronic structure of Graphene Oxide thin films at different stages of the thermal reduction process. It is established that the edge plane carboxyl groups are highly unstable, whereas carbonyl groups are more difficult to remove. The results consistently support the formation of phenol groups through reaction of basal plane epoxide groups with adjacent hydroxyl groups at moderate degrees of thermal activation (~400 {\deg}C). The phenol groups are predominant over carbonyl groups and survive even at a temperature of 1000 {\deg}C. For the first time a drastic increase in the density of states (DOS) near the Fermi level at 600 {\deg}C is observed, suggesting a progressive restoration of aromatic structure in the thermally reduced graphene oxideComment: Pagona Papakonstantinou as Corresponding author, E-mail: [email protected]

Computational studies for reduced graphene oxide in hydrogen-rich environment

We employ molecular dynamic simulations to study the reduction process of graphene-oxide (GO) in a chemically active environment enriched with hydrogen. We examine the concentration and pressure of hydrogen gas as a function of temperature in which abstraction of oxygen is possible with minimum damage to C-sp$^2$ bonds hence preserving the integrity of the graphene sheet. Through these studies we find chemical pathways that demonstrate beneficiary mechanisms for the quality of graphene including formation of water as well as suppression of carbonyl pair holes in favor of hydroxyl and epoxy formation facilitated by hydrogen gas in the environment.Comment: 9 pages and 9 figures. Animations and movies are available at: http://qmsimulatorgojpc.wordpress.com

Graphene Oxide-Gallic Acid Nanodelivery System for Cancer Therapy

Despite the technological advancement in the biomedical science, cancer remains a life-threatening disease. In this study, we designed an anticancer nanodelivery system using graphene oxide (GO) as nanocarrier for an active anticancer agent gallic acid (GA). The successful formation nanocomposite (GOGA) was characterized using XRD, FTIR, HRTEM, Raman, and UV/Vis spectroscopy. The release study shows that the release of GA from the designed anticancer nanocomposite (GOGA) occurs in a sustained manner in phosphate-buffered saline (PBS) solution at pH 7.4. In in vitro biological studies, normal fibroblast (3T3) and liver cancer cells (HepG2) were treated with different concentrations of GO, GOGA, and GA for 72 h. The GOGA nanocomposite showed the inhibitory effect to cancer cell growth without affecting normal cell growth. The results of this research are highly encouraging to go further for in vivo studies