Influence of atmospheric species on the electrical properties of functionalized graphene sheets.

We report on the time-dependent influence of atmospheric species on the electrical properties of functionalized graphene sheets (FGSs). When exposed to laboratory air, FGSs exhibit a significant, irreversible decrease in electrical conductance with time, strongly depending on the oxygen content of the FGSs. To separate the roles of charge carrier density and mobility in this aging process, we performed electron transport measurements using a back-gate field-effect transistor architecture.

Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime.

Intrinsic Catalytic Activity of Graphene Defects for the Co(II/III)(bpy)3 Dye-Sensitized Solar Cell Redox Mediator.

We demonstrate that functionalized graphene, rich with lattice defects but lean with oxygen sites, catalyzes the reduction of Co(III)(bpy)3 as well as platinum does, exhibiting a rate of heterogeneous electron transfer, k0, of ∼6 × 10(-3) cm/s. We show this rate to be an order of magnitude higher than on oxygen-site-rich graphene oxide, and over 2 orders of magnitude higher than on the basal plane of graphite (as a surrogate for pristine graphene). Furthermore, dye-sensitized solar cells using defect-rich graphene monolayers perform similarly to those using platinum nanoparticles as the catalyst.

Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e.

Buckling of dielectric elastomeric plates for soft, electrically active microfluidic pumps.

Elastic instabilities, when properly implemented within soft, mechanical structures, can generate advanced functionality. In this work, we use the voltage-induced buckling of thin, flexible plates to pump fluids within a microfluidic channel. The soft electrodes that enable electrical actuation are compatible with fluids, and undergo large, reversible deformations.

Energetics of defects on graphene through fluorination.

Functionalized graphene sheets (FGSs) comprise a unique member of the carbon family, demonstrating excellent electrical conductivity and mechanical strength. However, the detailed chemical composition of this material is still unclear. Herein, we take advantage of the fluorination process to semiquantitatively probe the defects and functional groups on graphene surface.

Electrochemical sensing of nitric oxide with functionalized graphene electrodes.

The intrinsic electrocatalytic properties of functionalized graphene sheets (FGSs) in nitric oxide (NO) sensing are determined by cyclic voltammetry with FGS monolayer electrodes. The degrees of reduction and defectiveness of the FGSs are varied by employing different heat treatments during their fabrication. FGSs with intermediate degrees of reduction and high Raman ID to IG peak ratios exhibit an NO oxidation peak potential of 794 mV (vs 1 M Ag/AgCl), closely matching values obtained with a platinized Pt control (791 mV) as well as recent results from the literature on porous or biofunctionalized electrodes.

Dispersion stability of functionalized graphene in aqueous sodium dodecyl sulfate solutions.

The colloidal stability of functionalized graphene sheets (FGSs) in aqueous sodium dodecyl sulfate (SDS) solutions of different concentrations was studied by optical microscopy and ultraviolet-visible light absorption after first dispersing the FGSs ultrasonically. In up to ∼10 μM SDS solutions, FGSs reaggregated within a few minutes, forming ramified structures in the absence of SDS and increasingly compact structures as the amount of SDS increased. Above ∼10 μM, the rate of reaggregation decreased with increasing SDS concentration; above ∼40 μM, the suspensions were colloidally stable for over a year.

Cementation of colloidal particles on electrodes in a galvanic microreactor.

We have studied the processes leading to the cementation of colloidal particles during their autonomous assembly on corroding copper electrodes within a Cu-Au galvanic microreactor. We determined the onset of particle immobilization through particle tracking, monitored the dissolution of copper as well as the deposition of insoluble products of the corrosion reactions in situ, and showed that particle immobilization initiated after reaction products (RPs) began to deposit on the electrode substrate. We further demonstrated that the time and the extent of RP precipitation and thus the strength of the particle-substrate bond could be tuned by varying the amount of copper in the system and the microreactor pH.

Adsorption of sodium dodecyl sulfate on functionalized graphene measured by conductometric titration.

We report on the adsorption of sodium dodecyl sulfate (SDS) onto functionalized graphene sheets (FGSs) in an aqueous system, measured at broad SDS and FGS concentration ranges by conductometric surfactant titration. At dilute SDS concentrations (<12 μM in bulk solution), there is evidence of a counterion exchange between hydronium ions (from the dissociation of acidic chemical functionalities on FGS) and sodium ions coadsorbing with dodecyl sulfate monomers onto FGSs. We find that, for FGS with a carbon-to-oxygen ratio of ~18, monolayer adsorption of SDS on FGS reaches full surface coverage by ~12 μM SDS.

Directed motion of colloidal particles in a galvanic microreactor.

The mechanisms leading to the deposition of colloidal particles in a copper-gold galvanic microreactor are investigated. Using in situ current density measurements and particle velocimetry, we establish correlations between the spatial arrangement and the geometry of the electrodes, current density distribution, and particle aggregation behavior. Ionic transport phenomena are responsible for the occurrence of strongly localized high current density at the edges and corners of the copper electrodes at large electrode separation, leading to a preferential aggregation of colloidal particles at the electrode edges.

Enhanced thermal decomposition of nitromethane on functionalized graphene sheets: ab initio molecular dynamics simulations.

The burning rate of the monopropellant nitromethane (NM) has been observed to increase by adding and dispersing small amounts of functionalized graphene sheets (FGSs) in liquid NM. Until now, no plausible mechanisms for FGSs acting as combustion catalysts have been presented. Here, we report ab initio molecular dynamics simulations showing that carbon vacancy defects within the plane of the FGSs, functionalized with oxygen-containing groups, greatly accelerate the thermal decomposition of NM and its derivatives.

Functionalized graphene sheets as a versatile replacement for platinum in dye-sensitized solar cells.

Several techniques for fabricating functionalized graphene sheet (FGS) electrodes were tested for catalytic performance in dye-sensitized solar cells (DSSCs). By using ethyl cellulose as a sacrificial binder, and partially thermolyzing it, we were able to create electrodes which exhibited lower effective charge transfer resistance (<1 Ω cm(2)) than the thermally decomposed chloroplatinic acid electrodes traditionally used. This performance was achieved not only for the triiodide/iodide redox couple, but also for the two other major redox mediators used in DSSCs, based on cobalt and sulfur complexes, showing the versatility of the electrode.

Hierarchically porous graphene as a lithium-air battery electrode.

The lithium-air battery is one of the most promising technologies among various electrochemical energy storage systems. We demonstrate that a novel air electrode consisting of an unusual hierarchical arrangement of functionalized graphene sheets (with no catalyst) delivers an exceptionally high capacity of 15000 mAh/g in lithium-O(2) batteries which is the highest value ever reported in this field. This excellent performance is attributed to the unique bimodal porous structure of the electrode which consists of microporous channels facilitating rapid O(2) diffusion while the highly connected nanoscale pores provide a high density of reactive sites for Li-O(2) reactions.

Local voltage drop in a single functionalized graphene sheet characterized by Kelvin probe force microscopy.

We studied the local voltage drop in functionalized graphene sheets of subμm size under external bias conditions by Kelvin probe force microscopy. Using this noninvasive experimental approach, we measured ohmic current-voltage characteristics and an intrinsic conductivity of about 3.7 × 10(5) S/m corresponding to a sheet resistance of 2.

Graphene-polypyrrole nanocomposite as a highly efficient and low cost electrically switched ion exchanger for removing ClO₄⁻ from wastewater.

Perchlorate (ClO(4)(-)) contamination is a widespread concern affecting water utilities. In the present study, functionalized graphene sheets were employed as the scaffold to synthesize a novel graphene-polypyrrole (Ppy) nanocomposite, which served as an excellent electrically switched ion exchanger for perchlorate removal. Scanning electron microscopy and electrochemical measurements showed that the 3D nanostructured graphene-Ppy nanocomposite exhibited a significantly improved uptake capacity for ClO(4)(-) compared with Ppy film alone.

High surface area tapes produced with functionalized graphene.

We describe a scalable method for producing continuous graphene networks by tape casting surfactant-stabilized aqueous suspensions of functionalized graphene sheets. Similar to all other highly connected graphene-containing networks, the degree of overlap between the sheets controls the tapes' electrical and mechanical properties. However, unlike other graphene-containing networks, the specific surface area of the cast tapes remains high (>400 m(2)·g(-1)).

Factors controlling the size of graphene oxide sheets produced via the graphite oxide route.

We have studied the effect of the oxidation path and the mechanical energy input on the size of graphene oxide sheets derived from graphite oxide. The cross-planar oxidation of graphite from the (0002) plane results in periodic cracking of the uppermost graphene oxide layer, limiting its lateral dimension to less than 30 μm. We use an energy balance between the elastic strain energy associated with the undulation of graphene oxide sheets at the hydroxyl and epoxy sites, the crack formation energy, and the interaction energy between graphene layers to determine the cell size of the cracks.

Sandwich-type functionalized graphene sheet-sulfur nanocomposite for rechargeable lithium batteries.

A functionalized graphene sheet-sulfur (FGSS) nanocomposite was synthesized as the cathode material for lithium-sulfur batteries. The structure has a layer of functionalized graphene sheets/stacks (FGS) and a layer of sulfur nanoparticles creating a three-dimensional sandwich-type architecture. This unique FGSS nanoscale layered composite has a high loading (70 wt%) of active material (S), a high tap density of ∼0.

Stabilization of electrocatalytic metal nanoparticles at metal-metal oxide-graphene triple junction points.

Carbon-supported precious metal catalysts are widely used in heterogeneous catalysis and electrocatalysis, and enhancement of catalyst dispersion and stability by controlling the interfacial structure is highly desired. Here we report a new method to deposit metal oxides and metal nanoparticles on graphene and form stable metal-metal oxide-graphene triple junctions for electrocatalysis applications. We first synthesize indium tin oxide (ITO) nanocrystals directly on functionalized graphene sheets, forming an ITO-graphene hybrid.

Tuning of structural color using a dielectric actuator and multifunctional compliant electrodes.

We have developed electrically conducting silicone elastomer nanocomposites that serve both as compliant electrodes in an electrostatic actuator and, at the same time, as optically active elements creating structural color. We demonstrate the capabilities of our setup by actuating an elastomeric diffraction grating and colloidal-crystal-based photonic structures.

Functionalized graphene as a catalytic counter electrode in dye-sensitized solar cells.

When applied on the counter electrode of a dye-sensitized solar cell, functionalized graphene sheets with oxygen-containing sites perform comparably to platinum (conversion efficiencies of 5.0 and 5.5%, respectively, at 100 mW cm(-2) AM1.

A graphene-based electrochemical sensor for sensitive detection of paracetamol.

An electrochemical sensor based on the electrocatalytic activity of functionalized graphene for sensitive detection of paracetamol is presented. The electrochemical behaviors of paracetamol on graphene-modified glassy carbon electrodes (GCEs) were investigated by cyclic voltammetry and square-wave voltammetry. The results showed that the graphene-modified electrode exhibited excellent electrocatalytic activity to paracetamol.