Ilhan A. Aksay

Functionalized graphene sheets for polymer nanocomposites

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.

Self-assembled TiO2-Graphene Hybrid Nanostructures for Enhanced Li-ion Insertion

We used anionic sulfate surfactants to assist the stabilization of graphene in aqueous solutions and facilitate the self-assembly of in situ grown nanocrystalline TiO2, rutile and anatase, with graphene. These nanostructured TiO2-graphene hybrid materials were used for investigation of Li-ion insertion properties. The hybrid materials showed significantly enhanced Li-ion insertion/extraction in TiO2. The specific capacity was more than doubled at high charge rates, as compared with the pure TiO2 phase. The improved capacity at high charge-discharge rate may be attributed to increased electrode conductivity in the presence of a percolated graphene network embedded into the metal oxide electrodes.

Glucose Oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing

Direct electrochemistry of a glucose oxidase (GOD)-graphene-chitosan nanocomposite was studied. The immobilized enzyme retains its bioactivity, exhibits a surface confined, reversible two-proton and two-electron transfer reaction, and has good stability, activity and a fast heterogeneous electron transfer rate with the rate constant (k(s)) of 2.83 s(-1). A much higher enzyme loading (1.12 x 10(-9)mol/cm(2)) is obtained as compared to the bare glass carbon surface. This GOD-graphene-chitosan nanocomposite film can be used for sensitive detection of glucose. The biosensor exhibits a wider linearity range from 0.08mM to 12mM glucose with a detection limit of 0.02mM and much higher sensitivity (37.93microAmM(-1)cm(-2)) as compared with other nanostructured supports. The excellent performance of the biosensor is attributed to large surface-to-volume ratio and high conductivity of graphene, and good biocompatibility of chitosan, which enhances the enzyme absorption and promotes direct electron transfer between redox enzymes and the surface of electrodes.

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) AM1.5G simulated light). To interpret the catalytic activity of functionalized graphene sheets toward the reduction of triiodide, we propose a new electrochemical impedance spectroscopy equivalent circuit that matches the observed spectra features to the appropriate phenomena. Using cyclic voltammetry, we also show that tuning our material by increasing the amount of oxygen-containing functional groups can improve its apparent catalytic activity. Furthermore, we demonstrate that a functionalized graphene sheet based ink can serve as a catalytic, flexible, electrically conductive counter electrode material.

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. Further, we show that the defects and functional groups on graphene favor the formation of isolated nanosized Li(2)O(2) particles and help prevent air blocking in the air electrode. The hierarchically ordered porous structure in bulk graphene enables its practical applications by promoting accessibility to most graphene sheets in this structure.

Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage.

Surfactant or polymer directed self-assembly has been widely investigated to prepare nanostructured metal oxides, semiconductors, and polymers, but this approach is mostly limited to two-phase materials, organic/inorganic hybrids, and nanoparticle or polymer-based nanocomposites. Self-assembled nanostructures from more complex, multiscale, and multiphase building blocks have been investigated with limited success. Here, we demonstrate a ternary self-assembly approach using graphene as fundamental building blocks to construct ordered metal oxide-graphene nanocomposites. A new class of layered nanocomposites is formed containing stable, ordered alternating layers of nanocrystalline metal oxides with graphene or graphene stacks. Alternatively, the graphene or graphene stacks can be incorporated into liquid-crystal-templated nanoporous structures to form high surface area, conductive networks. The self-assembly method can also be used to fabricate free-standing, flexible metal oxide-graphene nanocomposite films and electrodes. We have investigated the Li-ion insertion properties of the self-assembled electrodes for energy storage and show that the SnO2-graphene nanocomposite films can achieve near theoretical specific energy density without significant charge/discharge degradation.

Deformation mechanisms in nacre

Nacre (mother-of-pearl) from mollusc shells is a biologically formed lamellar ceramic. The inelastic deformation of this material has been experimentally examined, with a focus on understanding the underlying mechanisms. Slip along the lamellae tablet interface has been ascertained by testing in compression with the boundaries oriented at 45° to the loading axis. The steady-state shear resistance tss has been determined and inelastic strain shown to be as high as 8%. The inelastic deformation was realized by massive interlamellae shearing. Testing in tension parallel to the tablets indicates inelastic strain of about 1%, occurring at a steady-state stress, sss ∪ 110 MPa. The strain was associated with the formation of multiple dilatation bands at the intertablet boundaries accompanied by interlamellae sliding. Nano-asperities on the aragonite tablets and their interposing topology provide the resistance to interfacial sliding and establish the level of the stress needed to attain the inelastic strain. Detailed mechanisms and their significance for the design of robust ceramics are discussed.

Field-Induced Layering of Colloidal Crystals

An electrohydrodynamic methodology has been developed that makes possible the precise assembly of two- and three-dimensional colloidal crystals on electrode surfaces. Electrophoretically deposited colloidal particles were observed to move toward one another over very large distances (greater than five particle diameters) to form two-dimensional colloidal crystals for both micrometer- and nanometer-size particles. This coalescence of particles with the same charge is opposite to what is expected from electrostatic considerations and appears to result from electrohydrodynamic fluid flow arising from an ionic current flowing through the solution. The ability to modulate this “lateral attraction” between particles, by adjusting field strength or frequency, facilitates the reversible formation of two-dimensional fluid and crystalline colloidal states on the electrode surface. Further manipulation allows controlled structures to be assembled.

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. Platinum nanoparticles are then deposited, forming a unique triple-junction structure (Pt-ITO-graphene). Our experimental work and periodic density functional theory (DFT) calculations show that the supported Pt nanoparticles are more stable at the Pt-ITO-graphene triple junctions. Furthermore, DFT calculations suggest that the defects and functional groups on graphene also play an important role in stabilizing the catalysts. These new catalyst materials were tested for oxygen reduction for potential applications in polymer electrolyte membrane fuel cells, and they exhibited greatly enhanced stability and activity.

Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/graphene/chitosan nanocomposite film

The bionanocomposite film consisting of glucose oxidase/Pt/functional graphene sheets/chitosan (GOD/Pt/FGS/chitosan) for glucose sensing is described. With the electrocatalytic synergy of FGS and Pt nanoparticles to hydrogen peroxide, a sensitive biosensor with a detection limit of 0.6 microM glucose was achieved. The biosensor also has good reproducibility, long-term stability and negligible interfering signals from ascorbic acid and uric acid comparing with the response to glucose. The large surface area and good electrical conductivity of graphene suggests that graphene is a potential candidate as a sensor material. The hybrid nanocomposite glucose sensor provides new opportunity for clinical diagnosis and point-of-care applications.