Christian Punckt

Functionalized Graphene as a Catalytic Counter Electrode in Dye-Sensitized Solar Cells

When applied on the counter electrode of a dye-sensitized solar cell, functionalized graphene sheets with oxygen-containing sites perform comparably to platinum (conversion efficiencies of 5.0 and 5.5%, respectively, at 100 mW cm(-2) AM1.5G simulated light). To interpret the catalytic activity of functionalized graphene sheets toward the reduction of triiodide, we propose a new electrochemical impedance spectroscopy equivalent circuit that matches the observed spectra features to the appropriate phenomena. Using cyclic voltammetry, we also show that tuning our material by increasing the amount of oxygen-containing functional groups can improve its apparent catalytic activity. Furthermore, we demonstrate that a functionalized graphene sheet based ink can serve as a catalytic, flexible, electrically conductive counter electrode material.

The effect of degree of reduction on the electrical properties of functionalized graphene sheets

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 kΩ/sq) nonlinear current/voltage characteristics at low C/O to low-resistance (<10 kΩ/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.

Local Voltage Drop in a Single Functionalized Graphene Sheet Characterized by Kelvin Probe Force Microscopy

We studied the local voltage drop in functionalized graphene sheets of subμm size under external bias conditions by Kelvin probe force microscopy. Using this noninvasive experimental approach, we measured ohmic current-voltage characteristics and an intrinsic conductivity of about 3.7 × 10(5) S/m corresponding to a sheet resistance of 2.7 kΩ/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 × 10(-7) Ωcm(2).

Dielectric elastomer actuators with elastomeric electrodes

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.

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

The colloidal stability of functionalized graphene sheets (FGSs) in aqueous sodium dodecyl sulfate (SDS) solutions of different concentrations was studied by optical microscopy and ultraviolet-visible light absorption after first dispersing the FGSs ultrasonically. In up to ∼10 μM SDS solutions, FGSs reaggregated within a few minutes, forming ramified structures in the absence of SDS and increasingly compact structures as the amount of SDS increased. Above ∼10 μM, the rate of reaggregation decreased with increasing SDS concentration; above ∼40 μM, the suspensions were colloidally stable for over a year. The concentration of ∼40 μM SDS lies 2 orders of magnitude below the critical surface aggregation concentration of ∼1.8 mM SDS on FGSs but above the concentration (∼18 μM) 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.

Electrochemical sensing of nitric oxide with functionalized graphene electrodes.

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

Inhibition and Promotion of Copper Corrosion by CTAB in a Microreactor System

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 approximately 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.

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

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

Spreading of corrosion on stainless steel

In situ observations of pitting corrosion as it spreads across the surface of stainless steel were carried out. We apply two different imaging methods simultaneously, viz., ellipsomicroscopy for visualizing changes of surface film properties and contrast-enhanced microscopy for monitoring nucleation and reactivation of metastable corrosion pits. A correlation between oxide film weakening caused by individual pits and the nucleation of subsequent pits was found. The existence of front propagation as a component of the transition to pitting corrosion shows that characteristics of this process are consistent with the behavior of stochastic reaction-diffusion systems and that the onset of corrosion is a cooperative critical effect.

High frequency periodic forcing of the oscillatory catalytic CO oxidation on Pt (110)

Resonant periodic forcing is applied to catalytic CO oxidation on platinum (110) in the oscillatory regime. The external parameters are chosen such that the unperturbed system spontaneously develops chemical turbulence. By periodically modulating the CO partial pressure, changes in the spatiotemporal behaviour of the system can be induced: the turbulent behaviour is suppressed and frequency locked patterns with sub-harmonic entrainment develop. A novel gas-driving compressor has been implemented to perform the experimental work.