G. Kane Jennings

Graphene: Corrosion-Inhibiting Coating

We report the use of atomically thin layers of graphene as a protective coating that inhibits corrosion of underlying metals. Here, we employ electrochemical methods to study the corrosion inhibition of copper and nickel by either growing graphene on these metals, or by mechanically transferring multilayer graphene onto them. Cyclic voltammetry measurements reveal that the graphene coating effectively suppresses metal oxidation and oxygen reduction. Electrochemical impedance spectroscopy measurements suggest that while graphene itself is not damaged, the metal under it is corroded at cracks in the graphene film. Finally, we use Tafel analysis to quantify the corrosion rates of samples with and without graphene coatings. These results indicate that copper films coated with graphene grown via chemical vapor deposition are corroded 7 times slower in an aerated Na(2)SO(4) solution as compared to the corrosion rate of bare copper. Tafel analysis reveals that nickel with a multilayer graphene film grown on it corrodes 20 times slower while nickel surfaces coated with four layers of mechanically transferred graphene corrode 4 times slower than bare nickel. These findings establish graphene as the thinnest known corrosion-protecting coating.

Functionalized nanoporous gold leaf electrode films for the immobilization of photosystem I.

Plants and some types of bacteria demonstrate an elegant means to capitalize on the superabundance of solar energy that reaches our planet with their energy conversion process called photosynthesis. Seeking to harness Natures optimization of this process, we have devised a biomimetic photonic energy conversion system that makes use of the photoactive protein complex Photosystem I, immobilized on the surface of nanoporous gold leaf (NPGL) electrodes, to drive a photoinduced electric current through an electrochemical cell. The intent of this study is to further the understanding of how the useful functionality of these naturally mass-produced, biological light-harvesting complexes can be integrated with nonbiological materials. Here, we show that the protein complexes retain their photonic energy conversion functionality after attachment to the nanoporous electrode surface and, further, that the additional PSI/electrode interfacial area provided by the NPGL allows for an increase in PSI-mediated electron transfer with respect to an analogous 2D system if the pores are sufficiently enlarged by dealloying. This increase of interfacial area is pertinent for other applications involving electron transfer between phases; thus, we also report on the widely accessible and scalable method by which the NPGL electrode films used in this study are fabricated and attached to glass and Au/Si supports and demonstrate their adaptability by modification with various self-assembled monolayers. Finally, we demonstrate that the magnitude of the PSI-catalyzed photocurrents provided by the NPGL electrode films is dependent upon the intensity of the light used to irradiate the electrodes.

Photosystem I – Based biohybrid photoelectrochemical cells

Photosynthesis is the process by which Nature coordinates a tandem of protein complexes of impressive complexity that function to harness staggering amounts of solar energy on a global scale. Advances in biochemistry and nanotechnology have provided tools to isolate and manipulate the individual components of this process, thus opening a door to a new class of highly functional and vastly abundant biological resources. Here we show how one of these components, Photosystem I (PSI), is incorporated into an electrochemical system to yield a stand-alone biohybrid photoelectrochemical cell that converts light energy into electrical energy. The cells make use of a dense multilayer of PSI complexes assembled on the surface of the cathode to produce a photocatalytic effect that generates photocurrent densities of approximately 2 microA/cm(2) at moderate light intensities. We describe the relationship between the current and voltage production of the cells and the photoinduced interactions of PSI complexes with electrochemical mediators, and show that the performance of the present device is limited by diffusional transport of the electrochemical mediators through the electrolyte. These biohybrid devices display remarkable stability, as they remain active in ambient conditions for at least 280 days. Even at bench-scale production, the materials required to fabricate the cells described in this manuscript cost approximately 10 cents per cm(2) of active electrode area.

Rapid assembly of photosystem I monolayers on gold electrodes.

Photosystem I (PSI) has drawn widespread interest for use in biomimetically inspired energy conversion devices upon extracting it from plants or cyanobacteria and assembling it at surfaces. Here, we demonstrate that a critically dense monolayer of spinach-derived PSI must be formed on an electrode surface to achieve optimal photocurrents, and we introduce a new method for preparing these dense PSI monolayers that reduces the time required for assembly by approximately 80-fold in comparison to that for adsorption from solution. This method consists of applying a vacuum above the aqueous PSI solution during assembly to concentrate PSI and precipitate it into a thick layer onto the surface of various self-assembled monolayers or directly onto the electrode surface. Rinsing with water yields a dense monolayer of PSI that draws approximately 100 nA/cm2 of light-induced current from the gold electrode in the presence of appropriate mediators.

Enhanced Photocurrents of Photosystem I Films on p‐Doped Silicon

Tuning the Fermi energy of silicon through doping leads to alignment of silicon bands with the redox active sites of photosystem I. Integrating photosystem I films with p-doped silicon results in the highest reported photocurrent enhancement for a biohybrid electrode based on photosystem I.

Patterned nanoporous gold as an effective SERS template

We demonstrate large area two-dimensional arrays of patterned nanoporous gold for use as easy-to-fabricate, cost-effective, and stable surface enhanced Raman scattering (SERS) templates. Using a simple one-step direct imprinting process, subwavelength nanoporous gold (NPG) gratings are defined by densifying appropriate regions of a NPG film. Both the densified NPG and the two-dimensional grating pattern are shown to contribute to the SERS enhancement. The resulting substrates exhibit uniform SERS enhancement factors of at least 10(7) for a monolayer of adsorbed benzenethiol molecules.

Tribological durability of silane monolayers on silicon.

We report the frictional performance and long-term tribological stability of various alkyl silane monolayer films on silicon by using pin-on-disk tribometry at ambient conditions. We show that the durability of monolayers derived from n-alkyltrichlorosilanes on silicon increases exponentially with the chain length of the silane precursor, which we relate to the cohesive energy of these monolayers through molecular dynamics simulations. X-ray photoelectron spectroscopy (XPS) was used to show that tribological damage consisted of the loss of molecular components that could be partially replaced upon exposure to a solution containing perfluorinated silane precursors. For monolayers derived from n-octadecyltrichlorosilane, a critical load was identified to be approximately 250 mN (200 MPa), above which failure of films occurred within 100 cycles of testing. Monolayers with hydroxyl surfaces exhibited reduced stabilities due to stronger tip-surface interactions. Monolayers with the capability for cross-linking exhibited much greater stabilities than monolayers where cross-linking was limited or prevented. Collectively, these results demonstrate that the mechanical durability of monolayers when subjected to a tribological load is greatly enhanced by maximizing dispersional interactions and cross-linking and minimizing tip-surface interactions.

Photosystem I on Graphene as a Highly Transparent, Photoactive Electrode

We report the fabrication of a hybrid light-harvesting electrode consisting of photosystem I (PSI) proteins extracted from spinach and adsorbed as a monolayer onto electrically contacted, large-area graphene. The transparency of graphene supports the choice of an opaque mediator at elevated concentrations. For example, we report a photocurrent of 550 nA/cm(2) from a monolayer of PSI on graphene in the presence of 20 mM methylene blue, which yields an opaque blue solution. The PSI-modified graphene electrode has a total thickness of less than 10 nm and demonstrates photoactivity that is an order of magnitude larger than that for unmodified graphene, establishing the feasibility of conjoining these nanomaterials as potential constructs in next-generation photovoltaic devices.

Frictional Dynamics of Alkylsilane Monolayers on SiO2: Effect of 1-n-Butyl-3-methylimidazolium Nitrate as a Lubricant

The effect of 1-n-butyl-3-methylimidazolium nitrate ionic liquid (IL) on the shear dynamics and tribological properties of contacting ordered alkylsilane self-assembled monolayers (SAM) on SiO(2) surfaces was studied using molecular dynamics simulation. Use of the IL as a lubricant was found to reduce the friction between the contacting monolayers in the studied range of applied loads. At low applied loads, complex behavior in the dependency of the frictional force on the normal load in both lubricated and dry monolayers is observed and is shown to be due to the rearrangement of the SAM chains under shear. In contrast, this dependency was found to be linear at high normal loads. The simulations also indicate that the ordering of the SAM chains may be disrupted by penetrating lubricant molecules, suggesting that the IL could incorporate into a damaged area of the SAM coating and restore tribological properties. To our knowledge, this is the first simulation study of the effect of an IL lubricant on the frictional dynamics of SAMs.

Electrical Control of near-Field Energy Transfer between Quantum Dots and Two-Dimensional Semiconductors

We investigate near-field energy transfer between chemically synthesized quantum dots (QDs) and two-dimensional semiconductors. We fabricate devices in which electrostatically gated semiconducting monolayer molybdenum disulfide (MoS2) is placed atop a homogeneous self-assembled layer of core-shell CdSSe QDs. We demonstrate efficient nonradiative Förster resonant energy transfer (FRET) from QDs into MoS2 and prove that modest gate-induced variation in the excitonic absorption of MoS2 leads to large (∼500%) changes in the FRET rate. This in turn allows for up to ∼75% electrical modulation of QD photoluminescence intensity. The hybrid QD/MoS2 devices operate within a small voltage range, allow for continuous modification of the QD photoluminescence intensity, and can be used for selective tuning of QDs emitting in the visible-IR range.