Publications by Type: Journal Article

2017
Alifierakis, M. ; Sallah, K. S. ; Aksay, I. A. ; Prevost, J. H. Reversible Cluster Aggregation and Growth Model for Graphene Suspensions. AIChE Journal 2017, 63, 5462-5473.Abstract
We present a reversible cluster aggregation model for 2-D macromolecules represented by line segments in 2-D; and, we use it to describe the aggregation process of functionalized graphene particles in an aqueous SDS surfactant solution. The model produces clusters with similar sizes and structures as a function of SDS concentration in agreement with experiments and predicts the existence of a critical surfactant concentration (C-crit) beyond which thermodynamically stable graphene suspensions form. Around C-crit, particles form dense clusters rapidly and sediment. At C << C-crit, a contiguous ramified network of graphene gel forms which also densifies, but at a slower rate, and sediments with time. The deaggregation-reaggregation mechanism of our model captures the restructuring of the large aggregates towards a graphite-like structure for the low SDS concentrations. (C) 2017 American Institute of Chemical Engineers
2016
Uralcan, B. ; Aksay, I. A. ; Debenedetti, P. G. ; Limmer, D. T. Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions. Journal of Physical Chemistry Letters 2016, 7 2333-2338.Abstract
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. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.
Bozym, D. J. ; Korkut, S. ; Pope, M. A. ; Aksay, I. A. Dehydrated Sucrose Nanoparticles as Spacers for Graphene-Ionic Liquid Supercapacitor Electrodes. ACS Sustainable Chemistry & Engineering 2016, 4 7167-7174.Abstract
The addition of dehydrated sucrose nano particles increases the gravimetric capacitance of electrochemical double-layer capacitor electrodes produced via the evaporative consolidation of graphene oxide-water-ionic liquid gels by more than two-fold. Dehydrated sucrose adsorbs onto graphene oxide and serves as a spacer, preventing the graphene oxide from restacking during solvent evaporation. Despite 61 wt % of the solids being electrochemically inactive dehydrated sucrose nanoparticles, the best electrodes achieved an energy density of similar to 13.3 Wh/kg, accounting for the total mass of all electrode components.
Roy-Mayhew, J. D. ; Pope, M. A. ; Punckt, C. ; Aksay, I. A. Intrinsic Catalytic Activity of Graphene Defects for the Co-II/III(bpy)(3) Dye-Sensitized Solar Cell Redox Mediator. ACS Applied Materials & Interfaces 2016, 8 9134-9141.Abstract
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, k(0), of similar to 6 x 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.
Punckt, C. ; Pope, M. A. ; Liu, Y. F. M. ; Aksay, I. A. Structure-Dependent Electrochemistry of Reduced Graphene Oxide Monolayers. Journal of the Electrochemical Society 2016, 163, H491-H498.Abstract
While graphene and other carbonaceous nanomaterials have shown promise in a variety of electrochemical applications, measurement of their intrinsic performance is often confounded with effects related to the complexities due to diffusion in a porous medium. To by-pass this limitation, we use effectively non-porous tiled monolayers of reduced graphene oxide as a model platform to study how rates of heterogeneous electron transfer evolve as a function of graphene structure/chemistry. A variety of electrochemical systems are investigated including the standard ferri/ferrocyanide redox probe, several common biomolecular redox systems as well as copper electrodeposition. We show that the rates of heterogeneous electron transfer can vary by as much as 3 orders of magnitude depending on the reduction or annealing conditions used and the redox system investigated. Performance changes are linked to graphene chemistry, and we show that the graphene oxide reduction procedure must be chosen judiciously to maximize the electrochemical performance for particular applications. (C) 2016 The Electrochemical Society. All rights reserved.
2015
Bozym, D. J. ; Uralcan, B. ; Limmer, D. T. ; Pope, M. A. ; Szamreta, N. J. ; Debenedetti, P. G. ; Aksay, I. A. Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents. J. Phys. Chem. Lett. 2015, 6 2644-2648.Abstract

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., ∼ 1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low- dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

Zhang, C. ; Dabbs, D. M. ; Liu, L. - M. ; Aksay, I. A. ; Car, R. ; Selloni, A. Combined Effects of Functional Groups, Lattice Defects, and Edges in the Infrared Spectra of Graphene Oxide. J. Phys. Chem. C 2015, 119, 18167-18176.Abstract

Infrared spectroscopy in combination with density functional theory calculations has been widely used to characterize the structure of graphene oxide and its reduced forms. Yet, the synergistic effects of different functional groups, lattice defects, and edges on the vibrational spectra are not well understood. Here, we report first-principles calculations of the infrared spectra of graphene oxide performed on realistic, thermally equilibrated, structural models that incorporate lattice vacancies and edges along with various oxygen-containing functional groups. Models including adsorbed water are examined as well. Our results show that lattice vacancies lead to important blue and red shifts in the OH stretching and bending bands, respectively, whereas the presence of adsorbed water leaves these shifts largely unaffected. We also find unique infrared features for edge carboxyls resulting from interactions with both nearby functional groups and the graphene lattice. Comparison of the computed vibrational properties to our experiments clarifies the origin of several observed features and provides evidence that defects and edges are essential for characterizing and interpreting the infrared spectrum of graphene oxide.

Pope, M. A. ; Aksay, I. A. Four-Fold Increase in the Intrinsic Capacitance of Graphene through Functionalization and Lattice Disorder. J. Phys. Chem. C 2015, 119, 20369-20378.Abstract

Graphene has been heralded as a promising electrode material for high energy and power density electrochemical supercapacitors. This is in spite of recent work confirming the low double-layer capacitance (CDL) of the graphene/electrolyte interface limited by graphene’s low quantum capacitance (CQ), an effect known for the basal plane of graphite for over four decades. Consistent with this limit, much of the supercapacitor research implies the use of pristine graphene but, in contrast, uses a functionalized and defective graphene formed through the reduction of graphene oxide, without clarifying why reduced graphene oxide is needed to achieve high capacitance. Herein, we show that an optimal level of functionalization and lattice disorder in reduced graphene oxide yields a 4-fold increase in CDL over that of pristine graphene, suggesting graphene-based materials can indeed be tailored to engineer electrodes with significantly higher gravimetric capacitance limits exceeding 450 F/g than what has been achieved (∼ 274 F/g) thus far, even in nonaqueous electrolytes capable of high voltage operation.

Li, Y. ; Alain-Rizzo, V. ; Galmiche, L. ; Audebert, P. ; Miomandre, F. ; Louarn, G. ; Bozlar, M. ; Pope, M. A. ; Dabbs, D. M. ; Aksay, I. A. Functionalization of Graphene Oxide by Tetrazine Derivatives: A Versatile Approach toward Covalent Bridges between Graphene Sheets. Chem. Mater. 2015, 27, 4298-4310.Abstract

We have covalently grafted tetrazine derivatives to graphene oxide through nucleophilic substitution. Since the tetrazine unit is electroactive and nitrogen-rich, with a reduction potential sensitive to the type of substituent and degree of substitution, we used electrochemistry and X-ray photoelectron spectroscopy to demonstrate clear evidence for grafting through covalent bonding. Chemical modification was supported by Fourier transform infrared spectroscopy and thermal analysis. Tetrazines grafted onto graphene oxide displayed different mass losses compared to unmodified graphene and were more stable than the molecular precursors. Finally, a bridging tetrazine derivative was grafted between sheets of graphene oxide to demonstrate that the separation distance between sheets can be maintained while designing new graphene-based materials, including chemically bound, redox structures.

Hsieh, A. G. ; Punckt, C. ; Aksay, I. A. High-Rate Li+ Storage Capacity of Surfactant-Templated Graphene-TiO2 Nanocomposites. J. Electrochem. Soc. 2015, 162, A1566-A1573.Abstract
Graphene-TiO2 nanocomposites are a promising anode material for Li-ion batteries due to their good high-rate capacity, inherent safety, and mechanical and chemical robustness. However, despite a large number of scientific reports on the material, the mechanism of the enhanced high-rate Li+ storage capacity that results from the addition of graphene to TiO2 – typically attributed to improved electrical conductivity – is still not well understood. In this work, we focus on optimizing the processing of surfactant-templated graphene-TiO2 hybrid nanocomposites. Towards this end, we examine the influence of various processing parameters, in particular the surfactant-mediated colloidal dispersion of graphene, on the material properties and electrochemical performance of graphene-TiO2. We investigate the influence of electrode mass loading on Li+ storage capacity, focusing mainly on high-rate performance. Furthermore, we demonstrate an approach for estimating power loss during charge/discharge cycling, which offers a succinct method for characterizing the high-rate performance of Li-ion battery electrodes.
Pope, M. A. ; Aksay, I. A. Structural Design of Cathodes for Li-S Batteries. Adv. Energy Mater. 2015, 5 1500124.Abstract

Battery technologies involving Li-S chemistries have been touted as one of the most promising next generation systems. The theoretical capacity of sulfur is nearly an order of magnitude higher than current Li-ion battery insertion cathodes and when coupled with a Li metal anode, Li-S batteries promise specific energies nearly five-fold higher. However, this assertion only holds if sulfur cathodes could be designed in the same manner as cathodes for Li-ion batteries. Here, the recent efforts to engineer high capacity, thick, sulfur-based cathodes are explored. Various works are compared in terms of capacity, areal mass loading, and fraction of conductive additive, which are the critical parameters dictating the potential for a device to achieve a specific energy higher than current Li-ion batteries (i.e., >200 Wh kg−1 ). While an inferior specific energy is projected in the majority of cases, several promising strategies have the potential to achieve >500 Wh kg−1 . The challenges associated with the limited cycle-life of these systems due to both the polysulfide shuttle phenomenon and the rapid degradation of the Li metal anode that is experienced at the current densities required to charge high specific energy batteries in a reasonable timeframe are also discussed.

Lee, Y. J. ; Huang, L. ; Wang, H. ; Sushko, M. L. ; Schwenzer, B. ; Aksay, I. A. ; Liu, J. Structural rearrangement and dispersion of functionalized graphene sheets in aqueous solutions. Colloids Interf. Sci. Comm. 2015, 8 1-5. Publisher's VersionAbstract

Surfactants are widely used for dispersing graphene and functionalized graphene sheets (FGS) in colloidal suspensions, but there have been few studies of the structure of the dispersed graphene–surfactant complexes in suspension and of their time evolution. Here, we combine experimental study of efficiencies of ionic surfactants/polymers in suspending FGS in water with characterization using atomic force microscopy, small angle neutron scattering, and molecular simulations to probe the detailed structures of FGSs. The small angle scattering technique provides quantitative measurement of structure of graphene sheets in the solution. This study suggests that in both ionic and nonionic surfactants, the dispersion tends to degrade over time through detachment of the surfactant molecules and structural rearrangements. Ionic surfactants with strong interfacial binding and large molecular weight increase the dispersing power by over an order of magnitude.

2014
Tavakol, B. ; Bozlar, M. ; Punckt, C. ; Froehlicher, G. ; Stone, H. A. ; Aksay, I. A. ; Holmes, D. P. Buckling of dielectric elastomeric plates for soft, electrically active microfluidic pumps. Soft Matter 2014, 10, 4789-4794.Abstract
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. We quantified the onset of voltage-induced buckling, and measured the flow rate within the microchannel. This embeddable, flexible microfluidic pump will aid in the generation of new stand-alone microfluidic devices that require a tunable flow rate.
Vijayakumar, M. ; Schwenzer, B. ; Shutthanandan, V. ; Hu, J. Z. ; Liu, J. ; Aksay, I. A. Elucidating graphene-ionic liquid interfacial region: A combined experimental and computational study. Nano Energy 2014, 3 152-158.Abstract
Graphene and ionic liquids are promising candidates for electrode materials and electrolytes, respectively, for modern energy storage devices such as supercapacitors. Understanding the interactions at the interfacial region between these materials is crucial for optimizing the overall performance and efficiency of supercapacitors. The interfacial region between graphene and an imidazolium-based ionic liquid is analyzed in a combined experimental and computational study. This dual approach reveals that the imidazolium-based cations mostly orient themselves parallel to the graphene surface due to pi-pi stacking interaction and form a primary interfacial layer, which is subsequently capped by a layer of anions from the ionic liquid. However, it also becomes apparent that the molecular interplay at the interfacial region is highly influenced by functional group defects on the graphene surface, in particular by hydroxyl groups. (C) 2012 Elsevier Ltd. All rights reserved.
Xiao, J. ; Meduri, P. ; Chen, H. H. ; Wang, Z. G. ; Gao, F. ; Hu, J. Z. ; Feng, J. ; Hu, M. ; Dai, S. ; Brown, S. ; et al. Energetics of Defects on Graphene through Fluorination. ChemSusChem 2014, 7 1295-1300.Abstract

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. Functionalized graphene sheets are used as substrate for low-temperature (<150 °C) direct fluorination. The fluorine content has been modified to investigate the formation mechanism of different functional groups such as CF, CF2, OCF2 and (C=O)F during fluorination. The detailed structure and chemical bonds are simulated by density functional theory (DFT) and quantified experimentally by nuclear magnetic resonance (NMR). The electrochemical properties of fluorinated graphene are also discussed extending the use of graphene from fundamental research to practical applications.

Roy-Mayhew, J. D. ; Aksay, I. A. Graphene Materials and Their Use in Dye-Sensitized Solar Cells. Chemical Reviews 2014, 114, 6323-6348.
Punckt, C. ; Pope, M. A. ; Aksay, I. A. High Selectivity of Porous Graphene Electrodes Solely Due to Transport and Pore Depletion Effects. Journal of Physical Chemistry C 2014, 118, 22635-22642.Abstract
We contrast the performance of monolayer electrodes and thin porous film electrodes of highly reduced functionalized graphene to demonstrate that the introduction of electrode porosity gives rise to strong apparent electrocatalytic effects resulting in vastly improved electrode selectivity. This is despite graphene showing no intrinsic advantage over glassy carbon electrodes when used as a monolayer. The simultaneous electrooxidation of ascorbic acid, dopamine and uric acid is used as an experimental model electrolyte system. Our results suggest that a large number of reports claiming the superior surface chemistry of carbon nanomaterials as the reason for outstanding electrochemical characteristics should be revisited considering electrode morphology as a significant contributor to the observed behavior. Our experimental results are supported by numerical simulations explaining the porosity-induced electrode selectivity by the dominance of pore depletion over diffusion-limited currents.
2013
Hsieh, A. G. ; Punckt, C. ; Korkut, S. ; Aksay, I. A. Adsorption of Sodium Dodecyl Sulfate on Functionalized Graphene Measured by Conductometric Titration. Journal of Physical Chemistry B 2013, 117, 7950-7958.Abstract
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 mu M 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 similar to 18, monolayer adsorption of SDS on FGS reaches full surface coverage by similar to 12 mu M SDS. Additionally, the critical surface aggregation concentration (csac) for surface micelle formation on FGS is measured to be similar to 1.5 mM SDS The transition from monolayer adsorption to surface micelle formation appears to occur at a similar SDS concentration on FGSs as on graphite, suggesting there is little difference in the surfactant adsorption behavior on both materials. We estimate that the FGS surface area available for SDS adsorption is similar to 600 m(2)/g which is significantly less than expected for FGSs in suspension and indicates the presence of regions on FGS on which SDS adsorption does not occur.
Jan, L. ; Punckt, C. ; Aksay, I. A. Cementation of Colloidal Particles on Electrodes in a Galvanic Microreactor. ACS Applied Materials & Interfaces 2013, 5 6346-6353.Abstract
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 rnicroreactor. 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. The ability to cement colloidal particles at locations undergoing corrosion illustrates that the studied colloidal assembly approach holds potential for applications in dynamic material property adaptation.
Jan, L. ; Punckt, C. ; Khusid, B. ; Aksay, I. A. Directed Motion of Colloidal Particles in a Galvanic Microreactor. Langmuir 2013, 29, 2498-2505.Abstract
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. Preferential aggregation appears to be the result of a combination of electrophoretic effects and changes in bulk electrolyte flow patterns. We demonstrate that electrolyte flow is most likely driven by electrochemical potential gradients of reaction products formed during the inhomogeneous copper dissolution.
Hsieh, A. G. ; Korkut, S. ; Punckt, C. ; Aksay, I. A. Dispersion Stability of Functionalized Graphene in Aqueous Sodium Dodecyl Sulfate Solutions. Langmuir 2013, 29, 14831-14838.Abstract
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 similar to 10 mu M 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 similar to 10 mu M, the rate of reaggregation decreased with increasing SDS concentration; above similar to 40 mu M, the suspensions were colloidally stable for over a year. The concentration of similar to 40 mu M SDS lies 2 orders of magnitude below the critical surface aggregation concentration of similar to 1.8 mM SDS on FGSs but above the concentration (similar to 18 mu M) at which SDS begins to form a monolayer on FGSs. Neither surface micelle nor dense monolayer coverage is therefore required to obtain stable aqueous FGS dispersions. We support our experimental results by calculating the van der Waals and electrostatic interaction energies between FGSs as a function of SDS concentration and show that the experimentally observed transition from an unstable to a stable dispersion correlates with a transition from negative to positive interaction energies between FGSs in the aggregated state. Furthermore, our calculations support experimental evidence that aggregates tend to develop a compact structure over time.
Punckt, C. ; Muckel, F. ; Wolff, S. ; Aksay, I. A. ; Chavarin, C. A. ; Bacher, G. ; Mertin, W. The effect of degree of reduction on the electrical properties of functionalized graphene sheets. Applied Physics Letters 2013, 102.Abstract
We study the effect of carbon to oxygen ratio (C/O) on the electrical resistance of functionalized graphene sheets prepared by thermal exfoliation and reduction of graphite oxide at various temperatures. Using a 2-probe technique in conjunction with Kelvin probe force microscopy, we observe a transition from high-resistance (>400 k Omega/sq) nonlinear current/voltage characteristics at low C/O to low-resistance (<10 k Omega/sq) linear behavior at high C/O, indicating a transition from hopping to diffusive electron transport. Simultaneously, the metal-graphene contacts change from high-resistance Schottky-type behavior to nearly non-invasive metal-metal contact characteristics. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4775582]
Punckt, C. ; Pope, M. A. ; Aksay, I. A. On the Electrochemical Response of Porous Functionalized Graphene Electrodes. Journal of Physical Chemistry C 2013, 117, 16076-16086.Abstract
Electrodes used in electroanalysis, which are based on carbonaceous nanomaterials such as carbon nanotubes or graphene, often exhibit large degrees of porosity. By systematically varying the morphology of functionalized graphene electrodes from nearly flat to highly porous, we demonstrate experimentally that minute amounts of electrode porosity have surprisingly significant effects on the apparent reaction kinetics as determined by cyclic voltammetry, both in the reversible and the irreversible regime. We quantify electrode porosity using a coulometric approach and, with the help of numerical simulations, determine the correlation between electrode pore volume and apparent electrode kinetics. We show that in the reversible and quasi-reversible regime, the voltamperometric response constitutes a superposition of thin film diffusion-related effects within the porous electrode and of the standard flat electrode response. For irreversible kinetics, however, we show that diffusive coupling between the electrode and the electrolyte can, under suitably chosen conditions, result in effective electrocatalytic behavior. Confirming past theoretical work by Compton and others, our experiments demonstrate that for a comparison of electroanalytical data obtained with different electrode materials it is not sufficient to only consider differences in the materials' chemical structure but equally important to take into account differences in electrode morphology.
Liu, Y. F. M. ; Punckt, C. ; Pope, M. A. ; Gelperin, A. ; Aksay, I. A. Electrochemical Sensing of Nitric Oxide with Functionalized Graphene Electrodes. ACS Applied Materials & Interfaces 2013, 5 12624-12630.Abstract
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 I-D to I-G 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. We show that the peak potential obtained with FGS electrodes can be further reduced to 764 mV by incorporation of electrode porosity using a drop-casting approach, indicating a stronger apparent electrocatalytic effect on porous FGS electrodes as compared to platinized Pt. Taking into consideration effects of electrode Morphology, we thereby demonstrate that FGSs are intrinsically as catalytic toward NO oxidation as platinum. The lowered peak potential of porous FGS electrodes is accompanied by a significant increase in peak current, which we attribute either to pore depletion effects or an amplification effect due to subsequent electrooxidation reactions. Our results suggest that the development of sensor electrodes with higher sensitivity and lower detection limits should be feasible with FGSs.
Pope, M. A. ; Korkut, S. ; Punckt, C. ; Aksay, I. A. Supercapacitor Electrodes Produced through Evaporative Consolidation of Graphene Oxide-Water-Ionic Liquid Gels. Journal of the Electrochemical Society 2013, 160, A1653-A1660.Abstract
We use colloidal gels of graphene oxide in a water-ethanol-ionic liquid solution to assemble graphene-ionic liquid laminated structures for use as electrodes in electrochemical double layer capacitors. Our process involves evaporation of water and ethanol yielding a graphene oxide/ionic liquid composite, followed by thermal reduction of the graphene oxide to electrically conducting functionalized graphene. This yields an electrode in which the ionic liquid serves not only as the working electrolyte but also as a spacer to separate the graphene sheets and to increase their electrolyte-accessible surface area. Using this approach, we achieve an outstanding energy density of 17.5 Wh/kg at a gravimetric capacitance of 156 F/g and 3 V operating voltage, due to a high effective density of the active electrode material of 0.46 g/cm(2). By increasing the ionic liquid content and the degree of thermal reduction, we obtain electrodes that retain >90% of their capacitance at a scan rate of 500 mV/s, illustrating that we can tailor the electrodes toward higher power density if energy density is not the primary goal. The elimination of the electrolyte infiltration step from manufacturing makes,this bottom-up assembly approach scalable and well-suited for combinations of potentially any graphene material with ionic liquid electrolytes. (C) 2013 The Electrochemical Society. All rights reserved.
2012
Punckt, C. ; Jan, L. ; Jiang, P. ; Frewen, T. A. ; Saville, D. A. ; Kevrekidis, I. G. ; Aksay, I. A. Autonomous colloidal crystallization in a galvanic microreactor. Journal of Applied Physics 2012, 112.Abstract
We report on a technique that utilizes an array of galvanic microreactors to guide the assembly of two-dimensional colloidal crystals with spatial and orientational order. Our system is comprised of an array of copper and gold electrodes in a coplanar arrangement, immersed in a dilute hydrochloric acid solution in which colloidal micro-spheres of polystyrene and silica are suspended. Under optimized conditions, two-dimensional colloidal crystals form at the anodic copper with patterns and crystal orientation governed by the electrode geometry. After the aggregation process, the colloidal particles are cemented to the substrate by co-deposition of reaction products. As we vary the electrode geometry, the dissolution rate of the copper electrodes is altered. This way, we control the colloidal motion as well as the degree of reaction product formation. We show that particle motion is governed by a combination of electrokinetic effects acting directly on the colloidal particles and bulk electrolyte flow generated at the copper-gold interface. (C) 2012 American Institute of Physics.
Bozlar, M. ; Punckt, C. ; Korkut, S. ; Zhu, J. ; Foo, C. C. ; Suo, Z. G. ; Aksay, I. A. Dielectric elastomer actuators with elastomeric electrodes. Applied Physics Letters 2012, 101.Abstract
For many applications of dielectric elastomer actuators, it is desirable to replace the carbon-grease electrodes with stretchable, solid-state electrodes. Here, we attach thin layers of a conducting silicone elastomer to prestrained films of an acrylic dielectric elastomer and achieve voltage-actuated areal strains over 70%. The influence of the stiffness of the electrodes and the prestrain of the dielectric films is studied experimentally and theoretically. (C) 2012 American Institute of Physics.
Liu, L. M. ; Car, R. ; Selloni, A. ; Dabbs, D. M. ; Aksay, I. A. ; Yetter, R. A. Enhanced Thermal Decomposition of Nitromethane on Functionalized Graphene Sheets: Ab Initio Molecular Dynamics Simulations. Journal of the American Chemical Society 2012, 134, 19011-19016.Abstract
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, fimctionalized with oxygen-containing groups, greatly accelerate the thermal decomposition of NM and its derivatives. This occurs through reaction pathways involving the exchange of protons or oxygens between the oxygen-containing functional groups and NM and its derivatives. FGS initiates and promotes the decomposition of the monopropellant and its derivatives, ultimately forming H2O, CO2, and N-2. Concomitantly, oxygen-containing functional groups on the FGSs are consumed and regenerated without significantly changing the FGSs in accordance with experiments indicating that the FGSs are not consumed during combustion.
Roy-Mayhew, J. D. ; Boschloo, G. ; Hagfeldt, A. ; Aksay, I. A. Functionalized Graphene Sheets as a Versatile Replacement for Platinum in Dye-Sensitized Solar Cells. ACS Applied Materials & Interfaces 2012, 4 2794-2800.Abstract
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 Omega 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. DSSCs using these FGS electrodes had efficiencies (eta) equal to or higher than those using thermally decomposed chloroplatinic acid electrodes in each of the three major redox mediators: I (eta(FGS) = 6.8%, eta(Pt) = 6.8%), Co (4.5%, 4.4%), S (3.5%, 2.0%). Through an analysis of the thermolysis of the binder and composite material, we determined that the high surface area of an electrode, as determined by nitrogen adsorption, is consistent with but not sufficient for high performing electrodes. Two other important considerations are that (i) enough residue remains in the composite to maintain structural stability and prevent restacking of FGSs upon the introduction of the solvent, and (ii) this residue must not disperse in the electrolyte.
Li, X. L. ; Qi, W. ; Mei, D. H. ; Sushko, M. L. ; Aksay, I. ; Liu, J. Functionalized Graphene Sheets as Molecular Templates for Controlled Nucleation and Self-Assembly of Metal Oxide-Graphene Nanocomposites. Advanced Materials 2012, 24, 5136-5141.
Dabbs, D. M. ; Aksay, I. A. Multifunctional and Low-Density Inorganic Nanocomposites. JOM 2012, 64, 226-233.Abstract
We summarize our recent studies on the use of low-density nanoporous silica structures prepared through templating of a self-assembling disordered liquid-crystalline L (3) phase, as a matrix for use in numerous applications, including sensing, optical data storage, drug release, and structural. The silica matrix exhibits low density (0.5 g cm(-3) to 0.8 g cm(-3) for monoliths, 0.6 g cm(-3) to 0.99 g cm(-3) for fibers) coupled with high surface areas (up 1400 m(2) g(-1)) and void volumes (65% or higher). High-surface-area coatings are used to increase the sensitivity of mass-detecting quartz crystal microbalances to over 4000 times that of uncoated crystals. Monoliths, films, and fibers are produced using the templated silica gel. Once dried and converted to silica, the nanostructured material exhibits high fracture strength (up to 35 MPa in fibers) and Young's modulus (30 GPa to 40 GPa in fibers). These values are, respectively, two orders of magnitude and twice those of nanostructured silicas having comparable densities.
Ozbas, B. ; O'Neill, C. D. ; Register, R. A. ; Aksay, I. A. ; Prud'homme, R. K. ; Adamson, D. H. Multifunctional elastomer nanocomposites with functionalized graphene single sheets. Journal of Polymer Science Part B-Polymer Physics 2012, 50, 910-916.Abstract
We demonstrate the use of functionalized graphene sheets (FGSs) as multifunctional nanofillers to improve mechanical properties, lower gas permeability, and impart electrical conductivity for several distinct elastomers. FGS consists mainly of single sheets of crumbled graphene containing oxygen functional groups and is produced by the thermal exfoliation of oxidized graphite (GO). The present investigation includes composites of FGS and three elastomers: natural rubber (NR), styrenebutadiene rubber, and polydimethylsiloxane (PDMS). All of these elastomers show similar and significant improvements in mechanical properties with FGS, indicating that the mechanism of property improvement is inherent to the FGS and not simply a function of chemical crosslinking. The decrease in gas permeability is attributed to the high aspect ratio of the FGS sheets. This creates a tortuous path mechanism of gas diffusion; fitting the permeability data to the Nielsen model yields an aspect ratio of similar to 1000 for the FGS. Electrical conductivity is demonstrated at FGS loadings as low as 0.08% in PDMS and reaches 0.3 S/m at 4 wt % loading in NR. This combination of functionalities imparted by FGS is shown to result from its high aspect ratio and carbon-based structure. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012
Ozbas, B. ; Toki, S. ; Hsiao, B. S. ; Chu, B. ; Register, R. A. ; Aksay, I. A. ; Prud'homme, R. K. ; Adamson, D. H. Strain-induced crystallization and mechanical properties of functionalized graphene sheet-filled natural rubber. Journal of Polymer Science Part B-Polymer Physics 2012, 50, 718-723.Abstract
The effects of functionalized graphene sheets (FGSs) on the mechanical properties and strain-induced crystallization of natural rubber (NR) are investigated. FGSs are predominantly single sheets of graphene with a lateral size of several hundreds of nanometers and a thickness of 1.5 nm. The effect of FGS and that of carbon black (CB) on the strain-induced crystallization of NR is compared by coupled tensile tests and X-ray diffraction experiments. Synchrotron X-ray scattering enables simultaneous measurements of stress and crystallization of NR in real time during sample stretching. The onset of crystallization occurs at significantly lower strains for FGS-filled NR samples compared with CB-filled NR, even at low loadings. Neat-NR exhibits strain-induced crystallization around a strain of 2.25, while incorporation of 1 and 4 wt % FGS shifts the crystallization to strains of 1.25 and 0.75, respectively. In contrast, loadings of 16 wt % CB do not significantly shift the critical strain for crystallization. Two-dimensional (2D) wide angle X-ray scattering patterns show minor polymer chain alignment during stretching, in accord with previous results for NR. Small angle X-ray scattering shows that FGS is aligned in the stretching direction, whereas CB does not show alignment or anisotropy. The mechanical properties of filled NR samples are investigated using cyclic tensile and dynamic mechanical measurements above and below the glass transition of NR. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012
2011
Pan, S. Y. ; Aksay, I. A. Factors Controlling the Size of Graphene Oxide Sheets Produced via the Graphite Oxide Route. ACS Nano 2011, 5 4073-4083.Abstract
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 mu m. 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. As the effective crack propagation rate in the cross-planar direction is an order of magnitude smaller than the edge-to-center oxidation rate, graphene oxide single sheets larger than those defined by the periodic cracking cell size are produced depending on the aspect ratio of the graphite particles. We also demonstrate that external energy input from hydrodynamic drag created by fluid motion or sonication, further reduces the size of the graphene oxide sheets through tensile stress buildup in the sheets.
Zhang, S. ; Shao, Y. Y. ; Liao, H. G. ; Liu, J. ; Aksay, I. A. ; Yin, G. P. ; Lin, Y. H. Graphene Decorated with PtAu Alloy Nanoparticles: Facile Synthesis and Promising Application for Formic Acid Oxidation. Chemistry of Materials 2011, 23, 1079-1081.
Zhang, S. ; Shao, Y. Y. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. Graphene-Polypyrrole Nanocomposite as a Highly Efficient and Low Cost Electrically Switched Ion Exchanger for Removing ClO4- from Wastewater. ACS Applied Materials & Interfaces 2011, 3 3633-3637.Abstract
Perchlorate (ClO4-) 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 ClO4- compared with Ppy film alone. X-ray photoelectron spectroscopy confirmed the uptake and release process of ClO4- in graphene-Ppy nanocomposite. In addition, the presence of graphene substrate resulted in high stability of graphene-Ppy nanocomposite during potential cycling. The present work provides a promising method for large scale water treatment.
Xiao, J. ; Mei, D. H. ; Li, X. L. ; Xu, W. ; Wang, D. Y. ; Graff, G. L. ; Bennett, W. D. ; Nie, Z. M. ; Saraf, L. V. ; Aksay, I. A. ; et al. Hierarchically Porous Graphene as a Lithium-Air Battery Electrode. Nano Letters 2011, 11, 5071-5078.Abstract
The lithium-ir 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 Li2O2 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.
Korkut, S. ; Roy-Mayhew, J. D. ; Dabbs, D. M. ; Milius, D. L. ; Aksay, I. A. High Surface Area Tapes Produced with Functionalized Graphene. ACS Nano 2011, 5 5214-5222.Abstract
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)). Exhibiting apparent densities between 0.15 and 0.51 g.cm(-3), with electrical conductivities up to 24 kS.m(-1) and tensile strengths over 10 MPa, these tapes exhibit the best combination of properties with respect to density heretofore observed for carbon-based papers, membranes, or films.
Pope, M. A. ; Punckt, C. ; Aksay, I. A. Intrinsic Capacitance and Redox Activity of Functionalized Graphene Sheets. Journal of Physical Chemistry C 2011, 115, 20326-20334.Abstract
We present a general method for characterizing the intrinsic electrochemical properties of graphene sheets, such as the specific double-layer capacitance, in the absence of porosity-related artifacts and uncertainties. By assembling densely tiled monolayers of electrically insulating or conductive functionalized graphene sheets onto electrode substrates (gold and highly oriented pyrolytic graphite), we demonstrate our ability to isolate their intrinsic electrochemical response in terms of surface-specific double-layer capacitance and redox behavior. Using this system, the electrochemical properties of various types of graphene can be directly compared without the need to take into account changes in electrode morphology and electrolyte accessibility arising because of varying material properties.
Yan, L. ; Punckt, C. ; Aksay, I. A. ; Mertin, W. ; Bacher, G. Local Voltage Drop in a Single Functionalized Graphene Sheet Characterized by Kelvin Probe Force Microscopy. Nano Letters 2011, 11, 3543-3549.Abstract
We studied the local voltage drop in functionalized graphene sheets of sub mu m 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 x 10(5) S/m corresponding to a sheet resistance of 2.7 k Omega/sq under ambient conditions for graphene produced via thermal reduction of graphite oxide. The contact resistivity between functionalized graphene and metal electrode was found. to be <6.3 x 10(-7) Omega cm(2).
Cao, Y. L. ; Li, X. L. ; Aksay, I. A. ; Lemmon, J. ; Nie, Z. M. ; Yang, Z. G. ; Liu, J. Sandwich-type functionalized graphene sheet-sulfur nanocomposite for rechargeable lithium batteries. Physical Chemistry Chemical Physics 2011, 13, 7660-7665.Abstract
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 similar to 0.92 g cm(-3), and a reversible capacity of similar to 505 mAh g(-1) (similar to 464 mAh cm(-3)) at a current density of 1680 mA g(-1) (1C). When coated with a thin layer of cation exchange Nafion film, the migration of dissolved polysulfide anions from the FGSS nanocomposite was effectively reduced, leading to a good cycling stability of 75% capacity retention over 100 cycles. This sandwich-structured composite conceptually provides a new strategy for designing electrodes in energy storage applications.
Kou, R. ; Shao, Y. Y. ; Mei, D. H. ; Nie, Z. M. ; Wang, D. H. ; Wang, C. M. ; Viswanathan, V. V. ; Park, S. ; Aksay, I. A. ; Lin, Y. H. ; et al. Stabilization of Electrocatalytic Metal Nanoparticles at Metal-Metal Oxide-Graphene Triple Junction Points. Journal of the American Chemical Society 2011, 133, 2541-2547.Abstract
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.
Castrillon, S. R. V. ; Giovambattista, N. ; Aksay, I. A. ; Debenedetti, P. G. Structure and Energetics of Thin Film Water. Journal of Physical Chemistry C 2011, 115, 4624-4635.Abstract
We present a molecular dynamics (MD) simulation study of the structure and energetics of thin films of water adsorbed on solid substrates at 240 K. By considering crystalline silica as a model hydrophilic surface, we systematically investigate the effect of film thickness on the hydrogen bonding, density, molecular orientation, and energy of adsorbed water films over a broad surface coverage range (delta). At the lowest coverage investigated (delta = 1 monolayer, >90% of water molecules form three hydrogen bonds (H-bonds) with surface silanol groups and none with other water molecules; when delta = 1 ML, the most probable molecular orientation is characterized by both the molecular dipole and the OH vectors being parallel to the surface. As 6 increases, water-water and water-surface interactions compete, leading to the appearance of an orientational structure near the solid-liquid interface characterized by the dipole moment pointing toward the silica surface. We find that the water-surface H-bond connectivity and energetics of the molecular layer nearest to the solid liquid interface do not change as delta increases. Interfacial water molecules, therefore, are able to reorient and form water-water H-bonds without compromising water-surface interactions. The surface-induced modifications to the orientational structure of the adsorbed film propagate up to similar to 1.4 nm from the solid-liquid interface when delta = 15.1 ML (a film that is similar to 2.3 run thick). For the thinner adsorbed films (delta <= 4.3 ML, thickness <= 0.8 nm) orientational correlations imposed by the solid liquid and liquid-vapor interfaces are observed throughout.
2010
Tang, Z. W. ; Wu, H. ; Cort, J. R. ; Buchko, G. W. ; Zhang, Y. Y. ; Shao, Y. Y. ; Aksay, I. A. ; Liu, J. ; Lin, Y. H. Constraint of DNA on Functionalized Graphene Improves its Biostability and Specificity. Small 2010, 6 1205-1209.
Punckt, C. ; Pope, M. A. ; Liu, J. ; Lin, Y. H. ; Aksay, I. A. Electrochemical Performance of Graphene as Effected by Electrode Porosity and Graphene Functionalization. Electroanalysis 2010, 22, 2834-2841.Abstract
Graphene-based electrodes have recently gained popularity due to their superior electrochemical properties. However, the exact mechanisms of electrochemical activity are not yet understood. Here, we present data from NADH oxidation and ferri/ferrocyanide redox probe experiments to demonstrate that both (i) the porosity of the graphene electrodes, as effected by the packing morphology, and (ii) the functional group and the lattice defect concentration play a significant role on their electrochemical performance.
Roy-Mayhew, J. D. ; Bozym, D. J. ; Punckt, C. ; Aksay, I. A. Functionalized Graphene as a Catalytic Counter Electrode in Dye-Sensitized Solar Cells. ACS Nano 2010, 4 6203-6211.Abstract
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) AM1.56 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.
Shao, Y. Y. ; Wang, J. ; Wu, H. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. Graphene Based Electrochemical Sensors and Biosensors: A Review. Electroanalysis 2010, 22, 1027-1036.Abstract
Graphene, emerging as a true 2-dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene-based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphene-based enzyme biosensors have been summarized in more detail; Graphene-based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.
Kang, X. H. ; Wang, J. ; Wu, H. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. A graphene-based electrochemical sensor for sensitive detection of paracetamol. Talanta 2010, 81, 754-759.Abstract
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. A quasi-reversible redox process of paracetamol at the modified electrode was obtained, and the over-potential of paracetamol decreased significantly compared with that at the bare GCE. Such electrocatalytic behavior of graphene is attributed to its unique physical and chemical properties, e.g., subtle electronic characteristics, attractive pi-pi interaction, and strong adsorptive capability. This electrochemical sensor shows an excellent performance for detecting paracetamol with a detection limit of 3.2 x 10(-8) M, a reproducibility of 5.2% relative standard deviation, and a satisfied recovery from 96.4% to 103.3%. The sensor shows great promise for simple, sensitive, and quantitative detection and screening of paracetamol. (C) 2010 Elsevier B.V. All rights reserved.
Shao, Y. Y. ; Zhang, S. ; Engelhard, M. H. ; Li, G. S. ; Shao, G. C. ; Wang, Y. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. Nitrogen-doped graphene and its electrochemical applications. Journal of Materials Chemistry 2010, 20, 7491-7496.Abstract
Nitrogen-doped graphene (N-graphene) is obtained by exposing graphene to nitrogen plasma. N-graphene exhibits much higher electrocatalytic activity toward oxygen reduction and H(2)O(2) reduction than graphene, and much higher durability and selectivity than the widely-used expensive Pt for oxygen reduction. The excellent electrochemical performance of N-graphene is attributed to nitrogen functional groups and the specific properties of graphene. This indicates that N-graphene is promising for applications in electrochemical energy devices (fuel cells, metal-air batteries) and biosensors.
Du, D. ; Zou, Z. X. ; Shin, Y. S. ; Wang, J. ; Wu, H. ; Engelhard, M. H. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. Sensitive Immunosensor for Cancer Biomarker Based on Dual Signal Amplification Strategy of Graphene Sheets and Multienzyme Functionalized Carbon Nanospheres. Analytical Chemistry 2010, 82, 2989-2995.Abstract
A novel electrochemical immunosensor for sensitive detection of cancer biomarker alpha-fetoprotein (AFP) is described that uses a graphene sheet sensor platform and functionalized carbon nanospheres (CNSs) labeled with horseradish peroxidase-secondary antibodies (HRP-Ab2). Greatly enhanced sensitivity for the cancer biomarker is based on a dual signal amplification strategy: first, the synthesized CNSs yielded a homogeneous and narrow size distribution, which allowed several binding events of HRP-Ab2 on each nanosphere. Enhanced sensitivity was achieved by introducing the multibioconjugates of HRP-Ab2-CNSs onto the electrode surface through "sandwich" immunoreactions. Second, functionalized graphene sheets used for the biosensor platform increased the surface area to capture a large amount of primary antibodies (Ab1), thus amplifying the detection response. On the basis of the dual signal amplification strategy of graphene sheets and the multienzyme labeling, the developed immunosensor showed a 7-fold increase in detection signal compared to the immunosensor without graphene modification and CNSs labeling. The proposed method could respond to 0.02 ng mL(-1) AFP with a linear calibration range from 0.05 to 6 ng mL(-1). This amplification strategy is a promising platform for clinical screening of cancer biomarkers and point-of-care diagnostics.
Wang, D. H. ; Kou, R. ; Choi, D. ; Yang, Z. G. ; Nie, Z. M. ; Li, J. ; Saraf, L. V. ; Hu, D. H. ; Zhang, J. G. ; Graff, G. L. ; et al. Ternary Self-Assembly of Ordered Metal Oxide-Graphene Nanocomposites for Electrochemical Energy Storage. ACS Nano 2010, 4 1587-1595.Abstract
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.
Fang, Z. H. ; Punckt, C. ; Leung, E. Y. ; Schniepp, H. C. ; Aksay, I. A. Tuning of structural color using a dielectric actuator and multifunctional compliant electrodes. Applied Optics 2010, 49, 6689-6696.Abstract
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. (C) 2010 Optical Society of America
2009
Punckt, C. ; Aksay, I. A. Dissolution dynamics of thin films measured by optical reflectance. Journal of Chemical Physics 2009, 131.Abstract
Measuring the dissolution dynamics of thin films in situ both with spatial and temporal resolution can be a challenging task. Available methods such as scanning electrochemical microscopy rely on scanning the specimen and are intrinsically slow. We developed a characterization technique employing only an optical microscope, a digital charge coupled device camera, and a computer for image processing. It is capable of detecting dissolution rates of the order of nm/min and has a spatial and temporal resolution which is limited by the imaging and recording setup. We demonstrate the capabilities of our method by analyzing the electrochemical dissolution of copper thin films on gold substrates in a mild hydrochloric acid solution. Due to its simplicity, our technique can be implemented in any laboratory and can be applied to a variety of systems such as thin film sensors or passive coatings.
Castrillon, S. R. V. ; Giovambattista, N. ; Aksay, I. A. ; Debenedetti, P. G. Effect of Surface Polarity on the Structure and Dynamics of Water in Nanoscale Confinement. Journal of Physical Chemistry B 2009, 113, 1438-1446.Abstract
We present a molecular dynamics simulation study of the structure and dynamics of water confined between silica surfaces using beta-cristobalite as a model template. We scale the surface Coulombic charges by means of a dimensionless number, k, ranging from 0 to 1, and thereby we can model systems ranging frorn hydrophobic apolar to hydrophilic, respectively. Both rotational and translational dynamics exhibit a nonmonotonic dependence on k characterized by a maximum in the in-plane diffusion coefficient, D-parallel to, at values between 0.6 and 0.8, and a minimum in the rotational relaxation time, tau(R), at k = 0.6. The slow dynamics observed in the proximity of the hydrophobic apolar surface are a consequence of beta-cristobalite templating an ice-like water layer. The fully hydrophilic surfaces (k = 1.0), on the other hand, result in slow interfacial dynamics due to the presence of dense but disordered water that forms strong hydrogen bonds with surface silanol groups. Confinement also induces decoupling between translational and rotational dynamics, as evidenced by the fact that TR attains values similar to that of the bulk, while D-parallel to is always lower than in the bulk. The decoupling is characterized by a more drastic reduction in the translational dynamics of water compared to rotational relaxation.
Kou, R. ; Shao, Y. Y. ; Wang, D. H. ; Engelhard, M. H. ; Kwak, J. H. ; Wang, J. ; Viswanathan, V. V. ; Wang, C. M. ; Lin, Y. H. ; Wang, Y. ; et al. Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction. Electrochemistry Communications 2009, 11, 954-957.Abstract
Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with the commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets.
Castrillon, S. R. V. ; Giovambattista, N. ; Aksay, I. A. ; Debenedetti, P. G. Evolution from Surface-Influenced to Bulk-Like Dynamics in Nanoscopically Confined Water. Journal of Physical Chemistry B 2009, 113, 7973-7976.Abstract
We use molecular dynamics simulations to study the influence of confinement on the dynamics of a nanoscopic water film at T = 300 K and rho = 1.0 g cm(-3). We consider two infinite hydrophilic (beta-cristobalite) silica surfaces separated by distances between 0.6 and 5.0 nm. The width of the region characterized by surface-dominated slowing down of water rotational dynamics is similar to 0.5 nm, while the corresponding width for translational dynamics is similar to 1.0 nm. The different extent of perturbation undergone by the in-plane dynamic properties is evidence of rotational-translational decoupling. The local in-plane rotational relaxation time and translational diffusion coefficient collapse onto confinement-independent "master" profiles as long as the separation d >= 1.0 nm. Long-tithe tails in the perpendicular component of the dipole moment autocorrelation function are indicative of anisotropic behavior in the rotational relaxation.
Sabourin, J. L. ; Dabbs, D. M. ; Yetter, R. A. ; Dryer, F. L. ; Aksay, I. A. Functionalized Graphene Sheet Colloids for Enhanced Fuel/Propellant Combustion. ACS Nano 2009, 3 3945-3954.Abstract
We have compared the combustion of the monopropellant nitromethane with that of nitromethane containing colloidal particles of functionalized graphene sheets or metal hydroxides. The linear steady-state burning rates of the monopropellant and colloidal suspensions were determined at room temperature, under a range of pressures (3.35-14.4 MPa) using argon as a pressurizing fluid. The ignition temperatures were lowered and burning rates increased for the colloidal suspensions compared to those of the liquid monopropellant alone, with the graphene sheet suspension having significantly greater burning rates (i.e., greater than 175%). The relative change in burning rate from neat nitromethane increased with increasing concentrations of fuel additives and decreased with increasing pressure until at high pressures no enhancement was found.
Wu, H. ; Wang, J. ; Kang, X. H. ; Wang, C. M. ; Wang, D. H. ; Liu, J. ; Aksay, I. A. ; Lin, Y. H. Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/graphene/chitosan nanocomposite film. Talanta 2009, 80, 403-406.Abstract
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 mu M 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.
Kang, X. H. ; Wang, J. ; Wu, H. ; Aksay, I. A. ; Liu, J. ; Lin, Y. H. Glucose Oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing. Biosensors & Bioelectronics 2009, 25, 901-905.Abstract
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 0.08 mM to 12 mM glucose with a detection limit of 0.02 mM and much higher sensitivity (37.93 mu A mM(-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.
Wang, D. H. ; Choi, D. W. ; Li, J. ; Yang, Z. G. ; Nie, Z. M. ; Kou, R. ; Hu, D. H. ; Wang, C. M. ; Saraf, L. V. ; Zhang, J. G. ; et al. Self-Assembled TiO2-Graphene Hybrid Nanostructures for Enhanced Li-Ion Insertion. ACS Nano 2009, 3 907-914.Abstract
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.
Hirata, Y. ; Hara, A. ; Aksay, I. A. Thermodynamics of densification of powder compact. Ceramics International 2009, 35, 2667-2674.Abstract
This paper established a necessary condition for the sintering of powder compacts by examining the total free energy balance in terms of the particle size, neck size and contact number. The thermodynamic analysis of the proposed model clarifies the relation of shrinkage (q) of powder compact-contact angle (phi)-relative density at a given dihedral angle (phi(e)) of a grain boundary. Faster densification proceeds in the region with a larger coordination number (n) of particles at a small q value. A large shrinkage is needed to eliminate the large pores formed in the structure of small n value. Full density can be achieved in the range of 117 degrees
2008
Schniepp, H. C. ; Kudin, K. N. ; Li, J. L. ; Prud'homme, R. K. ; Car, R. ; Saville, D. A. ; Aksay, I. A. Bending Properties of Single Functionalized Graphene Sheets Probed by Atomic Force Microscopy. ACS Nano 2008, 2 2577-2584.Abstract
We probe the bending characteristics of functionalized graphene sheets with the tip of an atomic force microscope. Individual sheets are transformed from a flat into a folded configuration. Sheets can be reversibly folded and unfolded multiple times, and the folding always occurs at the same location. This observation suggests that the folding and bending behavior of the sheets is dominated by pre-existing kink (or even fault) lines consisting of defects and/or functional groups.
Korkut, S. ; Saville, D. A. ; Aksay, I. A. Collodial Cluster Arrays by Electrohydrodynamic Printing. Langmuir 2008, 24, 12196-12201.Abstract
A "stable" electrohydrodynamic jet is used to print arrays of colloidal suspensions on hydrophobic surfaces. Printed lines break up into sessile drops, and capillary forces guide the self-assembly of colloidal particles during the evaporation of the liquid, resulting in arrays of colloidal single particles or particle clusters depending on the concentration of the suspensions. The clusters differ from those formed in the absence of a substrate when the number of particles is larger than three. Multiple structures are found for the same number of particles.
Korkut, S. ; Aksay, I. A. Comment on "Enhanced Stability of Electrohydrodynamic Jets through Gas Ionization" - Korkut and Aksay reply. Physical Review Letters 2008, 101.Abstract
A Reply to the Comment by Manuel Gamero-Castano.
Ristenpart, W. D. ; Jiang, P. ; Slowik, M. A. ; Punckt, C. ; Saville, D. A. ; Aksay, I. A. Electrohydrodynamic Flow and Colloidal Patterning near Inhomogeneities on Electrodes. Langmuir 2008, 24, 12172-12180.Abstract
Current density inhomogeneities on electrodes (of physical, chemical, or optical origin) induce long-range electrohydrodynamic fluid motion directed toward the regions of higher current density. Here, we analyze the flow and its implications for the orderly arrangement of colloidal particles as effected by this flow on patterned electrodes. A scaling analysis indicates that the flow velocity is proportional to the product of the applied voltage and the difference in current density between adjacent regions on the electrode. Exact analytical solutions for the streamlines are derived for the case of a spatially periodic perturbation in current density along the electrode. Particularly simple asymptotic expressions are obtained in the limits of thin double layers and either large or small perturbation wavelengths. Calculations of the streamlines are in good agreement with particle velocimetry experiments near a mechanically generated inhomogeneity (a "scratch") that generates a current density larger than that of the unmodified electrode. We demonstrate that proper placement of scratches on an electrode yields desired patterns of colloidal particles.
Korkut, S. ; Saville, D. A. ; Aksay, I. A. Enhanced stability of electrohydrodynamic jets through gas ionization. Physical Review Letters 2008, 100.Abstract
Theoretical predictions of the nonaxisymmetric instability growth rate of an electrohydrodynamic jet based on the measured total current overestimate experimental values. We show that this apparent discrepancy is the result of gas ionization in the surrounding gas and its effect on the surface charge density of the jet. As a result of gas ionization, a sudden drop in the instability growth rate occurs below a critical electrode separation, yielding highly stable jets that can be used for nano- to microscale printing.
Ramanathan, T. ; Abdala, A. A. ; Stankovich, S. ; Dikin, D. A. ; Herrera-Alonso, M. ; Piner, R. D. ; Adamson, D. H. ; Schniepp, H. C. ; Chen, X. ; Ruoff, R. S. ; et al. Functionalized graphene sheets for polymer nanocomposites. Nature Nanotechnology 2008, 3 327-331.Abstract
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(1). 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(2-11). 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 polyacrylonitrile) 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.
Murira, C. M. ; Punckt, C. ; Schniepp, H. C. ; Khusid, B. ; Aksay, I. A. Inhibition and Promotion of Copper Corrosion by CTAB in a Microreactor System. Langmuir 2008, 24, 14269-14275.Abstract
We report on an optical microscopy technique for the analysis of corrosion kinetics of metal thin films in microreactor systems and use it to study. the role of cetyltrimethylammonium bromide surfactant as a corrosion inhibitor in a copper-gold galvanic coplanar microsystem. A minimum in the dissolution rate of copper is observed when the surfactant concentration is similar to 0.8 mM. To explain why the inhibitory role of the surfactant does not extend to higher concentrations, we use zero resistance ammetry with separated half cells and show that while the surfactant inhibits cathodic reactions on gold, it also promotes the corrosion of copper because of the catalytic action of bromide counterions. These two competing processes lead to the observed minimum in the dissolution rate.
Poon, H. F. ; Saville, D. A. ; Aksay, I. A. Linear colloidal crystal arrays by electrohydrodynamic printing. Applied Physics Letters 2008, 93.Abstract
We use electrohydrodynamic jets of colloidal suspensions to produce arrays of colloidal crystalline stripes on surfaces. A critical factor in maintaining a stable jet is the distance of separation between the nozzle and the surface. Colloidal crystalline stripes are produced as two wetting lines of the deployed suspension merge during drying. To ensure that the two wetting lines merge, the "deployed-line-width" to "particle size" ratio is kept below a critical value so that the capillary forces overcome the frictional forces between the particles and the substrate. (C) 2008 American Institute of Physics.
Schniepp, H. C. ; Shum, H. C. ; Saville, D. A. ; Aksay, I. A. Orientational order of molecular assemblies on rough surfaces. Journal of Physical Chemistry C 2008, 112, 14902-14906.Abstract
Using atomic force microscopy, we show that previous observations on the orientational order of micelles on atomically smooth crystals with directions dictated by the crystal symmetry is only valid for the case of perfectly smooth crystals. On rough surfaces, orientations are independent of the lattice symmetry and the observed directions can be explained by considering the guiding influence of topographic surface features.
Kudin, K. N. ; Ozbas, B. ; Schniepp, H. C. ; Prud'homme, R. K. ; Aksay, I. A. ; Car, R. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Letters 2008, 8 36-41.Abstract
We investigate Raman spectra of graphite oxide and functionalized graphene sheets with epoxy and hydroxyl groups and Stone-Wales and 5-8-5 defects by first-principles calculations to interpret our experimental results. Only the alternating pattern of single-double carbon bonds within the sp(2) carbon ribbons provides a satisfactory explanation for the experimentally observed blue shift of the G band of the Raman spectra relative to graphite. To obtain these single-double bonds, it is necessary to have sp(3) carbons on the edges of a zigzag carbon ribbon.
Schniepp, H. C. ; Saville, D. A. ; Aksay, I. A. Tip-induced orientational order of surfactant micelles on gold. Langmuir 2008, 24, 626-631.Abstract
Using liquid-cell atomic force microscopy, we investigate aqueous solutions of alkyltrimethylammonium halide surfactants at the Au(III) surface. The long, micellar surfactant surface aggregates cover the gold surface completely and exhibit two types of orientational order for chloride and bromide counterions, respectively. We observe lateral forces perpendicular to the scanning direction, which we explain by anisotropic friction between the probe and the oriented micelles. Conversely, we show that these friction forces can be employed to modify the spatial conformation of the micellar adlayer. Where previous methods have failed to provide control over the orientation down to the level of individual micelles, we use this technique to achieve a very high degree of order over more than 100 micelle diameters.
2007
Ristenpart, W. D. ; Aksay, I. A. ; Saville, D. A. Electrically driven flow near a colloidal particle close to an electrode with a faradaic current. Langmuir 2007, 23, 4071-4080.Abstract
To elucidate the nature of processes involved in electrically driven particle aggregation in steady fields, flows near a charged spherical colloidal particle next to an electrode were studied. Electrical body forces in diffuse layers near the electrode and the particle surface drive an axisymmetric flow with two components. One is electroosmotic flow (EOF) driven by the action of the applied field on the equilibrium diffuse charge layer near the particle. The other is electrohydrodynamic (EHD) flow arising from the action of the applied field on charge induced in the electrode polarization layer. The EOF component is proportional to the current density and the particle surface (zeta) potential, whereas our scaling analysis shows that the EHD component scales as the product of the current density and applied potential. Under certain conditions, both flows are directed toward the particle, and a superposition of flows from two nearby particles provides a mechanism for aggregation. Analytical calculations of the two flow fields in the limits of infinitesimal double layers and slowly varying current indicate that the EOF and EHD flow are of comparable magnitude near the particle whereas in the far field the EHD flow along the electrode is predominant. Moreover, the dependence of EHD flow on the applied potential provides a possible explanation for the increased variability in aggregation velocities observed at higher field strengths.
Ku, A. Y. ; Saville, D. A. ; Aksay, I. A. Electric-field-induced orientation of surfactant-templated nanoscopic silica. Langmuir 2007, 23, 8156-8162.Abstract
While exhibiting a well-defined nanometer-level structure, surfactant-templated nanoscopic silicas produced via self-assembly do not always possess long-range order. We demonstrate that long-range order can be controlled by guiding the self-assembly of nanostructured silica-surfactant hybrids with low-strength electric fields (E similar to 200 V/m) to produce nanoscopic silica with both the micrometer- and nanometer-level structures oriented parallel to the applied field. Under the influence of the electric field, nanoscopic silica particles migrate, elongate, and merge into fibers with a rate of migration proportional to the applied field strength. The linear dependence with the field strength indicates that the process is governed by electroosmotic flow but not by polarization effects. Realignment of the short-range ordered surfactant nanochannels along the fiber axis accompanies the migration.
Ristenpart, W. D. ; Aksay, I. A. ; Saville, D. A. Electrohydrodynamic flow around a colloidal particle near an electrode with an oscillating potential. Journal of Fluid Mechanics 2007, 575, 83-109.Abstract
Electrohydrodynamic (EHD) flow around a charged spherical colloid near an electrode was studied theoretically and experimentally to understand the nature of long-range particle-particle attraction near electrodes. Numerical computations for finite double-layer thicknesses confirmed the validity of an asymptotic methodology for thin layers. Then the electric potential around the particle was computed analytically in the limit of zero Peclet number and thin double layers for oscillatory electric fields at frequencies where Faradaic reactions are negligible. Streamfunctions for the steady component of the EHD flow were determined with an electro-osmotic slip boundary condition on the electrode surface. Accordingly, it was established how the axisymmetric flow along the electrode is related to the dipole coefficient of the colloidal particle. Under certain conditions, the flow is directed toward the particle and decays as r(-4), in accord with observations of long-range particle aggregation. To test the theory, particle-tracking experiments were performed with fluorescent 300 nm particles around 50 mu m particles over a wide range of electric field strengths and frequencies. Treating the particle surface conductivity as a fitting parameter yields velocities in excellent agreement with the theoretical predictions. The observed frequency dependence, however, differs from the model predictions, suggesting that the effect of convection on the charge distribution is not negligible as assumed in the zero Peclet number limit.
Herrera-Alonso, M. ; Abdala, A. A. ; McAllister, M. J. ; Aksay, I. A. ; Prud'homme, R. K. Intercalation and stitching of graphite oxide with diaminoalkanes. Langmuir 2007, 23, 10644-10649.Abstract
The intercalation reaction of graphite oxide with diaminoalkanes, with the general formula H2N(CH2)(n)NH2 (n = 4-10), was studied as a method for synthesizing pillared graphite with tailored interlayer spacing. Interlayer spacings from 0.8 to 1.0 nm were tailored by varying the size of the intercalant from (CH2)(4) to (CH2)(10). X-ray diffraction and infrared spectroscopy were used to confirm intercalation, and the frequency of the CH2 stretch confirmed that the intercalants are in a disordered state, with an important contribution from the gauche conformer. Sequential intercalation of diaminoalkanes followed by dodecylamine demonstrated the inability of these "stitched" systems to undergo expansion along the c-direction, indicative of cross-linking. Finally, the reaction of graphite oxide with diaminoalkanes under reflux and for extended periods (> 72 h) resulted in the chemical reduction of the graphite oxide to a disordered graphitic structure.
Adamson, D. H. ; Dabbs, D. M. ; Pacheco, C. R. ; Giotto, M. V. ; Morse, D. E. ; Aksay, I. A. Non-peptide polymeric silicatein alpha mimic for neutral pH catalysis in the formation of silica. Macromolecules 2007, 40, 5710-5717.Abstract
We have synthesized a catalytically active polymer inspired by the naturally occurring protein silicatein alpha and have shown it to catalyze the formation of silica from tetraethoxysilane under near-neutral pH and ambient temperatures. We based the composition of the polymer on the functionalities found in silicatein alpha, specifically those essential components of the catalytically active site for the hydrolysis of silicon alkoxides. Our bioinspired polymer is a block copolymer of poly(2-vinylpyridine-b-1,2-butadiene), functionalized by the addition of hydroxyl groups via hydroboration chemistry. The catalytic action of our polymer on tetraethoxysilane at neutral pH and ambient temperature conditions has been confirmed using a modified molybdic acid assay method, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The structure of the resulting gel is investigated by scanning electron microscopy and solid-state nuclear magnetic resonance. The microscopic features of the material formed resemble that of gels formed by the acid-catalyzed hydrolysis of tetraethoxysilane.
McAllister, M. J. ; Li, J. L. ; Adamson, D. H. ; Schniepp, H. C. ; Abdala, A. A. ; Liu, J. ; Herrera-Alonso, M. ; Milius, D. L. ; Car, R. ; Prud'homme, R. K. ; et al. Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chemistry of Materials 2007, 19, 4396-4404.Abstract
A detailed analysis of the thermal expansion mechanism of graphite oxide to produce functionalized graphene sheets is provided. Exfoliation takes place when the decomposition rate of the epoxy and hydroxyl sites of graphite oxide exceeds the diffusion rate of the evolved gases, thus yielding pressures that exceed the van der Waals forces holding the graphene sheets together. A comparison of the Arrhenius dependence of the reaction rate against the calculated diffusion coefficient based on Knudsen diffusion suggests a critical temperature of 550 degrees C which must be exceeded for exfoliation to occur. As a result of their wrinkled nature, the functionalized and defective graphene sheets do not collapse back to graphite oxide but are highly agglomerated. After dispersion by ultrasonication in appropriate solvents, statistical analysis by atomic force microscopy shows that 80% of the observed flakes are single sheets.
Schniepp, H. C. ; Shum, H. C. ; Saville, D. A. ; Aksay, I. A. Surfactant aggregates at rough solid-liquid interfaces. Journal of Physical Chemistry B 2007, 111, 8708-8712.Abstract
We demonstrate improved atomic force microscopic imaging of surfactant surface aggregates, featuring an increase in the topography contrast by several hundred percent with respect to all previous studies. Surfactant aggregates on rough gold surfaces, which could not be imaged previously because of low resolution, display substantially different morphologies when compared with atomically smooth materials.
2006
Chun, J. ; Li, J. L. ; Car, R. ; Aksay, I. A. ; Saville, D. A. Anisotropic adsorption of molecular assemblies on crystalline surfaces. Journal of Physical Chemistry B 2006, 110, 16624-16632.Abstract
Orientational order of surfactant micelles and proteins on crystalline templates has been observed but, given that the template unit cell is significantly smaller than the characteristic size of the adsorbate, this order cannot be attributed to lattice epitaxy. We interpret the template-directed orientation of rodlike molecular assemblies as arising from anisotropic van der Waals interactions between the assembly and crystalline surfaces where the anisotropic van der Waals interaction is calculated using the Lifshitz methodology. Provided the assembly is sufficiently large, substrate anisotropy provides a torque that overcomes rotational Brownian motion near the surface. The probability of a particular orientation is computed by solving a Smoluchowski equation that describes the balance between van der Waals and Brownian torques. Torque aligns both micelles and protein fibrils; the interaction energy is minimized when the assembly lies perpendicular to a symmetry axis of a crystalline substrate. Theoretical predictions agree with experiments for both hemi-cylindrical micelles and protein fibrils adsorbed on graphite.
Chen, C. H. ; Saville, D. A. ; Aksay, I. A. Electrohydrodynamic "drop-and-place" particle deployment. Applied Physics Letters 2006, 88.Abstract
The "drop-and-place" paradigm aims at delivering and positioning liquid drops using a pulsed electrohydrodynamic jet. On-demand drops much smaller than the diameter of the delivery nozzle may also contain particles. We report proof-of-concept experiments on the delivery of single 2 mu m diameter particles using a 50 mu m nozzle and identify the control parameters for dosing and positioning accuracies. A positioning accuracy at the micrometer level is achieved by eliminating contact line pinning on a hydrophobic surface and minimizing impingement-induced motion. The dosing statistics follow the random Poisson distribution, indicating that single-particle accuracy can be achieved using a gating mechanism. (c) 2006 American Institute of Physics.
Bhansali, S. H. ; Jarvis, J. M. ; Aksay, I. A. ; Carbeck, J. D. Enhanced resonator sensitivity with nanostructured porous silica coatings. Langmuir 2006, 22, 6676-6682.Abstract
We present a strategy to increase the sensitivity of resonators to the presence of specific molecules in the gas phase, measured by the change in resonant frequency as the partial pressure of the molecule changes. We used quartz crystals as the resonators and coated them with three different thin films (< 1 mu m thick) of porous silica: silica xerogel, silica templated by an ordered hexagonal phase of surfactant micelles, and silica templated by an isotropic L-3 phase surfactant micellar system. We compared the sensitivity of coated resonators to the presence of water vapor. The crystals coated with hexagonal phase-templated silica displayed a sensitivity enhancement up to 100-fold compared to an uncoated quartz crystal in the low-pressure regime where adsorption played a dominant role. L-3 phase-templated silica displayed the highest sensitivity (up to a 4000-fold increase) in the high partial pressure regimes where capillary condensation was the main accumulation mechanism. Three parameters differentiate the contributions of these coatings to the sensitivity of the underlying resonator: (i) specific surface area per unit mass of the coating, (ii) accessibility of the surfaces to a target molecule, and (iii) distribution in the characteristic radii of curvature of internal surfaces, as measured by capillary condensation.
Schniepp, H. C. ; Li, J. L. ; McAllister, M. J. ; Sai, H. ; Herrera-Alonso, M. ; Adamson, D. H. ; Prud'homme, R. K. ; Car, R. ; Saville, D. A. ; Aksay, I. A. Functionalized single graphene sheets derived from splitting graphite oxide. Journal of Physical Chemistry B 2006, 110, 8535-8539.Abstract
A process is described to produce single sheets of functionalized graphene through thermal exfoliation of graphite oxide. The process yields a wrinkled sheet structure resulting from reaction sites involved in oxidation and reduction processes. The topological features of single sheets, as measured by atomic force microscopy, closely match predictions of first-principles atomistic modeling. Although graphite oxide is an insulator, functionalized graphene produced by this method is electrically conducting.
Saville, D. A. ; Chun, J. ; Li, J. L. ; Schniepp, H. C. ; Car, R. ; Aksay, I. A. Orientational order of molecular assemblies on inorganic crystals. Physical Review Letters 2006, 96.Abstract
Surfactant micelles form oriented arrays on crystalline substrates although registration is unexpected since the template unit cell is small compared to the size of a rodlike micelle. Interaction energy calculations based on molecular simulations reveal that orientational energy differences on a molecular scale are too small to explain matters. With atomic force microscopy, we show that orientational ordering is a dynamic, multimolecule process. Treating the cooperative processes as a balance between van der Waals torque on a large, rodlike micellar assembly and Brownian motion shows that orientation is favored.
Li, J. L. ; Kudin, K. N. ; McAllister, M. J. ; Prud'homme, R. K. ; Aksay, I. A. ; Car, R. Oxygen-driven unzipping of graphitic materials. Physical Review Letters 2006, 96.Abstract
Optical microscope images of graphite oxide (GO) reveal the occurrence of fault lines resulting from the oxidative processes. The fault lines and cracks of GO are also responsible for their much smaller size compared with the starting graphite materials. We propose an unzipping mechanism to explain the formation of cracks on GO and cutting of carbon nanotubes in an oxidizing acid. GO unzipping is initiated by the strain generated by the cooperative alignment of epoxy groups on a carbon lattice. We employ two small GO platelets to show that through the binding of a new epoxy group or the hopping of a nearby existing epoxy group, the unzipping process can be continued during the oxidative process of graphite. The same epoxy group binding pattern is also likely to be present in an oxidized carbon nanotube and cause its breakup.
Chen, C. H. ; Saville, D. A. ; Aksay, I. A. Scaling laws for pulsed electrohydrodynamic drop formation. Applied Physics Letters 2006, 89.Abstract
A pulsed electrohydrodynamic jet can produce on-demand drops much smaller than the delivery nozzle. This letter describes an experimentally validated model for electrically pulsed jets. Viscous drag in a thin nozzle limits the flow rate and leads to intrinsic pulsations of the cone jet. A scale analysis for intrinsic cone-jet pulsations is derived to establish the operating regime for drop deployment. The scaling laws are applicable to similar electrohydrodynamic processes in miniaturized electrospraying systems. (c) 2006 American Institute of Physics.
Schniepp, H. C. ; Saville, D. A. ; Aksay, I. A. Self-healing of surfactant surface micelles on millisecond time scales. Journal of the American Chemical Society 2006, 128, 12378-12379.
Malik, A. S. ; Dabbs, D. M. ; Katz, H. E. ; Aksay, I. A. Silica monoliths templated on L-3 liquid crystal. Langmuir 2006, 22, 325-331.Abstract
Dimensionally stable, optically clear, highly porous (similar to 65% of the apparent volume), and high surface area (up to 1400 m(2)/g) silica monoliths were fabricated as thick disks (0.5 cm) by templating the isotropic liquid crystalline L-3 phase with silica through the hydrolysis and condensation of a silicon alkoxide and then removing the organic constituents by supercritical ethanol extraction. The L3 liquid crystal is a stable phase formed by the cosurfactants cetylpyridinium chloride monohydrate and hexanol in HCl(aq) solvent. Extracted 0.5 cm thick disks exhibited a low ratio of scattered to transmitted visible light (1.5 x 10(-6) at 22 from the surface normal). The degree of silica condensation in the monoliths was high, as determined by Si-29 NMR measurements of Q(3) and Q(4) peak intensities (0.53 and 0.47, respectively). As a result, the extracted and dried monoliths were mechanically robust and did not fracture when infiltrated by organic solvents. Photoactive liquid monomers were infiltrated into extracted silica monoliths and polymerized in situ, demonstrating the possible application of templated silica to optical storage technology.
Dabbs, D. M. ; Mulders, N. ; Aksay, I. A. Solvothermal removal of the organic template from L-3 ("sponge") templated silica monoliths. Journal of Nanoparticle Research 2006, 8 603-614.Abstract
We compare the methods of continuous solvent (Soxhlet) and supercritical solvent extractions for the removal of the organic template from nanostructured silica monoliths. Our monoliths are formed by templating the L-3 liquid crystal phase of cetylpyridinium chloride in aqueous solutions with tetramethoxy silane. The monoliths that result from both Soxhlet and supercritical extraction methods are mechanically robust, optically clear, and free of cracks. The Soxhlet method compares favorably with supercritical solvent extraction in that equivalent L-3-templated silica can be synthesized without the use of specialized reactor hardware or higher temperatures and high pressures, while avoiding noxious byproducts. The comparative effectiveness of various solvents in the Soxhlet process is related to the Hildebrand solubility parameter, determined by the effective surface area of the extracted silica.
Bhansali, S. H. ; Malik, A. S. ; Jarvis, J. M. ; Akartuna, I. ; Dabbs, D. M. ; Carbeck, J. D. ; Aksay, I. A. The stability of L-3 sponge phase in acidic solutions. Langmuir 2006, 22, 4060-4064.Abstract
In the synthesis of the disordered lyotropic liquid crystalline L-3 sponge phase prepared with the cosurfactants cetylpyridinium chloride and hexanol, aqueous NaCl solution is used as the solvent. When this sponge phase is used as the template for L3 silica-phase processing, we replace NaCl with HCl to facilitate the acid catalysis of tetramethoxysilane in forming a templated silica gel, assuming that changing the solvent from NaCl(aq) to HCl(aq) of equivalent ionic strength does not affect the stability range of the L3 phase. In this work, we confirm that changing the pH of the solvent from neutral to acidic (with HQ has negligible effect on the L3 phase region. Equivalent ionic strength is provided by either NaCl(aq) or HCl(aq) solvent; therefore, a similar phase behavior is observed regardless of which aqueous solvent is used.
2005
Dabbs, D. M. ; Ramachandran, U. ; Lu, S. ; Liu, J. ; Wang, L. Q. ; Aksay, I. A. Inhibition of aluminum oxyhydroxide precipitation with citric acid. Langmuir 2005, 21, 11690-11695.Abstract
Citric acid has been shown to act as an agent for increasing the solubility of aluminum oxyhydroxides in aqueous solutions of high (>2.47 mol/mol) hydroxide-to-aluminum ratios. Conversely, citric acid also colloidally stabilizes particles in aqueous suspensions of aluminum-containing particles. Solutions of aluminum chloride, with and without citric acid added, were titrated with NaOH(aq), The presence and size of particles were determined using quasi-elastic light scattering. In solutions that contained no citric acid, particles formed instantaneously when NaOH(aq) was added but these were observed to rapidly diminish in size, disappearing at OH/Al ratios below 2.5 mol/mol. When the OH/Al ratio was raised beyond 2.5 by adding more NaOH(aq), suspensions of colloidally stable particles formed. Large polycations containing 13 aluminum atoms were detected by Al-27 solution NMR in citric-acid-free solutions with OH/Al ratios slightly lower than 2.5. In comparison, adding citric acid to solutions of aluminum chloride inhibited the formation of large aluminum-containing polycations. The absence of the polycations prevents or retards the subsequent formation of particles, indicating that the polycations, when present, act as seeds to the formation of new particles. Particles did not form in solutions with a citric acid/aluminum ratio of 0.8 until sufficient NaOH(aq) was added to raise the OH/Al ratio to 3.29. By comparison, lower amounts of citric acid did not prevent particles from forming but did retard the rate of growth.
Martin, C. R. ; Aksay, I. A. Microchannel molding: A soft lithography-inspired approach to micrometer-scale patterning. Journal of Materials Research 2005, 20, 1995-2003.Abstract
A new patterning technique for the deposition of sol-gels and chemical solution precursors was developed to address some of the limitations of soft lithography approaches. When using micromolding in capillaries to pattern precursors that exhibit large amounts of shrinkage during drying, topographical distortions develop. In place of patterning the elastomeric mold, the network of capillary channels was patterned directly into the substrate surface and an elastomer membrane is used to complete the channels. When the wetting properties of the substrate surfaces were carefully controlled using self-assembled monolayers (SAMs), lead zirconate titanate thin films with nearly rectangular cross-sections were successfully patterned. This technique, called microchannel molding (mu CM), also provided a method for aligning multiple layers such as bottom electrodes for device fabrication.
Li, J. L. ; Chun, J. ; Wingreen, N. S. ; Car, R. ; Aksay, I. A. ; Saville, D. A. Use of dielectric functions in the theory of dispersion forces. Physical Review B 2005, 71.Abstract
The modern theory of dispersion forces uses macroscopic dielectric functions epsilon(omega) as a central ingredient. We reexamined the formalism and found that at separation distance < 2 nm the full dielectric function epsilon(omega,k) is needed. The use of epsilon(omega,k) results in as much as 30% reduction of the calculated Hamaker constants reported in the current literature. At larger distances, the theory reduces to the traditional method, which uses dielectric functions in the long-wavelength limit. We illustrate the formalism using the example of interaction between two graphite slabs. This example is of importance for intercalation and exfoliation of graphite and for the use of exfoliated graphite in composite materials. The formalism can also be extended to study anisotropic van der Waals interactions.
2004
Ristenpart, W. D. ; Aksay, I. A. ; Saville, D. A. Assembly of colloidal aggregates by electrohydrodynamic flow: Kinetic experiments and scaling analysis. Physical Review E 2004, 69.Abstract
Electric fields generate transverse flows near electrodes that sweep colloidal particles into densely packed assemblies. We interpret this behavior in terms of electrohydrodynamic motion stemming from distortions of the field by the particles that alter the body force distribution in the electrode charge polarization layer. A scaling analysis shows how the action of the applied electric field generates fluid motion that carries particles toward one another. The resulting fluid velocity is proportional to the square of the applied field and decreases inversely with frequency. Experimental measurements of the particle aggregation rate accord with the electrohydrodynamic theory over a wide range of voltages and frequencies.
Abdala, A. A. ; Milius, D. L. ; Adamson, D. H. ; Aksay, I. A. ; Prudhomme, R. K. Inspired by abalone shell: Strengthening of porous ceramics with polymers. Polymeric Materials: Science & Engineering 2004, 90, 384-385.
Adamson, D. H. ; Dabbs, D. M. ; Aksay, I. A. ; Morse, D. E. Non-peptide, silicatein alpha inspired silica condensation catalyst. Polymeric Materials: Science & Engineering 2004, 90, 239-240.
Martin, C. R. ; Aksay, I. A. Submicrometer-scale patterning of ceramic thin films. Journal of Electroceramics 2004, 12, 53-68.Abstract
The patterning of ceramic thin films is of great interest for use in MEMS and other applications. However, the complex chemistries of certain materials make the use of traditional photolithography techniques prohibitive. In this paper, a number of low-cost, high throughput techniques for the patterning of ceramic thin films derived from chemical solution precursors, such as sol-gels and ceramic slurries, are presented. A particular emphasis is placed on methods that are derived from soft lithographic methods using elastomer molds. Two categories of techniques are discussed: first, the focus is on methods that rely on the principles of confinement within the physical features of the mold to define the pattern on the substrate surface. Then, subtractive patterning techniques that rely on transferring a pattern to a spin-cast, large-area continuous thin film are described. While most techniques have been demonstrated with fidelities on the order of 100 nm, their inability to precisely register and align the patterns as part of a hierarchical fabrication scheme have thus far hindered their commercial implementation.
2003
Ristenpart, W. D. ; Aksay, I. A. ; Saville, D. A. Electrically guided assembly of planar superlattices in binary colloidal suspensions. Physical Review Letters 2003, 90.Abstract
Binary colloidal suspensions are assembled into planar superlattices using ac electric fields. Either
triangular or square-packed arrays form, depending on the frequency and relative particle concentrations.
The frequency dependence is striking since superlattices develop at low and high frequencies
but not at intermediate frequencies. We explain the low frequency behavior <3 kHz in terms of
induced-dipole repulsion balanced by attraction resulting from electrohydrodynamic (EHD) flow. At
high frequencies (20–200 kHz), EHD flow is negligible but aggregation occurs since dipole-dipole
interactions become attractive.
Vartuli, J. S. ; Ozenbas, M. ; Chun, C. M. ; Trau, M. ; Aksay, I. A. Micropatterned lead zirconium titanate thin films. Journal of Materials Research 2003, 18, 1259-1265.Abstract
Micropatterning of Pb(Zr0.52Ti0.48)O3 (PZT) thin films with line features as small as
350 nm was demonstrated through capillary molding of organometallic solutions within
the continuous channels of an elastomeric mold. Despite the large stresses that develop
during the evaporation of the solvent, pyrolysis of the organics, and the densification
and crystallization of the inorganic gel, the patterned crystalline PZT films were
crack-free and mechanically robust. Flawless regions as large as 1 cm2 were obtained.
The cross-sectional shape of the patterned PZT lines was trapezoidlike. Single
perovskite PZT grains that formed during annealing at 600–700 °C completely filled
the cross-sectional area of the patterned lines. Lead acetate, zirconium propoxide, and
titanium isopropoxide were used as the starting materials. Substrates used included
silver tape, stainless steel plate, silicon wafer, and platinum-coated silicon wafer.
Gleason, N. J. ; Nodes, C. J. ; Higham, E. M. ; Guckert, N. ; Aksay, I. A. ; Schwarzbauer, J. E. ; Carbeck, J. D. Patterning proteins and cells using two-dimensional arrays of colloids. Langmuir 2003, 19, 513-518.Abstract
Asimple method is described for controlling the organization of proteins on surfaces using two-dimensional arrays of micron-sized colloidal particles. Suspensions of colloids functionalized with proteins are deposited onto coverslips coated with gold using a combination of gravitational settling and applied electrical fields. Varying settling time and particle concentration controls the density of particles on the substrate. Surface coverage ranged from an essentially continuous coating of protein on close-packed arrays to domains of protein separated by distances as large as 16 ím. Colloidal particle arrays were also patterned into 500 µm islands on substrates using elastomeric lift-off membranes. The applicability of this approach to the promotion of fibroblast cell adhesion and spreading was demonstrated using particles coated with the cell adhesion protein fibronectin. Behavior of adherent cells varied with particle density. This method provides a general strategy for controlling the organization of functional proteins at surfaces on three length scales: the size of individual colloidal particles, the spacing between particles, and the organization of particles in patterned arrays.

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