Diagnostic Criteria for the Characterization of Electrode Reactions with Chemically Coupled Reactions Preceding the Electron Transfer by Cyclic Square Wave Voltammetry.

Theory for cyclic square wave voltammetry of electrode reactions with chemical reactions preceding the electron transfer is presented. Theoretical voltammograms were calculated following systematic variation of empirical parameters to assess their impact on the shape of the voltammogram. From the trends obtained, diagnostic criteria for this mechanism were deduced. When properly applied, these criteria will enable non-experts in voltammetry to assign the electrode reaction mechanism and accurately measure reaction kinetics.

Electrostatic Force Microscopic Characterization of Early Stage Carbon Deposition on Nickel Anodes in Solid Oxide Fuel Cells.

Carbon deposition on nickel anodes degrades the performance of solid oxide fuel cells that utilize hydrocarbon fuels. Nickel anodes with BaO nanoclusters deposited on the surface exhibit improved performance by delaying carbon deposition (i.e., coking). The goal of this research was to visualize early stage deposition of carbon on nickel surface and to identify the role BaO nanoclusters play in coking resistance. Electrostatic force microscopy was employed to spatially map carbon deposition on nickel foils patterned with BaO nanoclusters. Image analysis reveals that upon propane exposure initial carbon deposition occurs on the Ni surface at a distance from the BaO features. With continued exposure, carbon deposits penetrate into the BaO-modified regions. After extended exposure, carbon accumulates on and covers BaO. The morphology and spatial distribution of deposited carbon was found to be sensitive to experimental conditions.

Cyclic Square Wave Voltammetry of Surface-Confined Quasireversible Electron Transfer Reactions.

The theory for cyclic square wave voltammetry of surface-confined quasireversible electrode reactions is presented and experimentally verified. Theoretical voltammograms were calculated following systematic variation of empirical parameters to assess their impact on the shape of the voltammogram. From the trends obtained, diagnostic criteria for this mechanism were deduced. These criteria were experimentally confirmed using two well-established surface-confined analytes. When properly applied, these criteria will enable non-experts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

An operando surface enhanced Raman spectroscopy (SERS) study of carbon deposition on SOFC anodes.

Thermally robust and chemically inert Ag@SiO2 nanoprobes are employed to provide the surface enhanced Raman scattering (SERS) effect for an in situ/operando study of the early stage of carbon deposition on nickel-based solid oxide fuel cell (SOFC) anodes. The enhanced sensitivity to carbon enables the detection of different stages of coking, offering insights into intrinsic coking tolerance of material surfaces. Application of a thin coating of gadolinium doped ceria (GDC) enhances the resistance to coking of nickel surfaces. The electrochemically active Ni-YSZ interface appears to be more active for hydrocarbon reforming, resulting in the accumulation of different hydrocarbon molecules, which can be readily removed upon the application of an anodic current. Operando SERS is a powerful tool for the mechanistic study of coking in SOFC systems. It is also applicable to the study of other catalytic and electrochemical processes in a wide range of conditions.

Effect of water absorption on pollen adhesion.

Pollens possess a thin liquid coating, pollenkitt, which plays a major role in adhesion by forming capillary menisci at interfaces. Unfortunately, the influence of humidity on pollenkitt properties and capillary adhesion is unknown. Because humidity varies widely in the environment, the answers have important implications for better understanding plant reproduction, allergy and asthma, and pollen as atmospheric condensation nuclei. Here, pollenkitt-mediated adhesion of sunflower pollen to hydrophilic and hydrophobic surfaces was measured as a function of humidity. The results quantify for the first time the significant water absorption of pollenkitt and the resulting complex dependence of adhesion on humidity. On hydrophilic Si, adhesion increased with increasing RH for pollens with or without pollenkitt, up to 200nN at 70% RH. In contrast, on hydrophobic PS, adhesion of pollenkitt-free pollen is independent of RH. Surprisingly, when pollenkitt was present adhesion forces on hydrophobic PS first increased with RH up to a maximum value at 35% RH (∼160nN), and then decreased with further increases in RH. Independent measurement of pollenkitt properties is used with models of capillary adhesion to show that humidity-dependent changes in pollenkitt wetting and viscosity are responsible for this complex adhesion behavior.

Diagnostic criteria for the characterization of quasireversible electron transfer reactions by cyclic square wave voltammetry.

Theory for cyclic square wave voltammetry of quasireversible electron transfer reactions is presented and experimentally verified. The impact of empirical parameters on the shape of the current-voltage curve is examined. From the trends, diagnostic criteria enabling the use of this waveform as a tool for mechanistic analysis of electrode reaction processes are presented. These criteria were experimentally confirmed using Eu(3+)/Eu(2+), a well-established quasireversible analyte. Using cyclic square wave voltammetry, both the electron transfer coefficient and rate were calculated for this analyte and found to be in excellent agreement with literature. When properly applied, these criteria will enable nonexperts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

Well-organized raspberry-like Ag@Cu bimetal nanoparticles for highly reliable and reproducible surface-enhanced Raman scattering.

Surface-enhanced Raman scattering (SERS) is ideally suited for probing and mapping surface species and incipient phases on fuel cell electrodes because of its high sensitivity and surface-selectivity, potentially offering insights into the mechanisms of chemical and energy transformation processes. In particular, bimetal nanostructures of coinage metals (Au, Ag, and Cu) have attracted much attention as SERS-active agents due to their distinctive electromagnetic field enhancements originated from surface plasmon resonance. Here we report excellent SERS-active, raspberry-like nanostructures composed of a silver (Ag) nanoparticle core decorated with smaller copper (Cu) nanoparticles, which displayed enhanced and broadened UV-Vis absorption spectra. These unique Ag@Cu raspberry nanostructures enable us to use blue, green, and red light as the excitation laser source for surface-enhanced Raman spectroscopy (SERS) with a large enhancement factor (EF). A highly reliable SERS effect was demonstrated using Rhodamine 6G (R6G) molecules and a thin film of gadolinium doped ceria.

Polystyrene beads as probes of the surface-enhanced Raman scattering response characteristics of silver nanorod arrays.

Polystyrene microspheres were used to interrogate the surface-enhanced Raman scattering (SERS) response of silver nanorod (AgNR) array substrates. It has been suggested that enhancement between nanorods is significantly greater than that at the top due to contributing electromagnetic fields from each nanostructure. To test this theory, two different sized fluorescent polystyrene microspheres were used. The SERS intensity of beads small enough to fit within the array was compared with that of larger beads confined to rest on top of the array. Location of the beads within the array was established using optical fluorescence and scanning electron microscopy. The findings presented herein suggest that evaporation of the sample produces a nonuniform distribution of scatterers across the AgNR array and that the enhancement found for beads located on top of the AgNRs was significantly greater than that for beads located within the array.

Limitations of surface enhanced Raman scattering in sensing DNA hybridization demonstrated by label-free DNA oligos as molecular rulers of distance-dependent enhancement.

This article presents a critical evaluation of silver nanorod arrays as substrates for assaying nucleic acid hybridization by surface enhanced Raman scattering (SERS). SERS spectra acquired on complementary oligos, alone or in combination, contain the known spectral signatures of the nucleotides that comprise the oligo; however, no signature bands characteristic of the hybrid were observed. Spectra acquired on an oligo with a 5'- or 3'-thiol were distinctly different from that acquired on the identical oligo without a thiol pendant group suggesting a degree of control over the orientation of the oligo on the nanorod surface. A set of oligos consisting of adenine tracts in a polycytosine chain served as molecular rulers to probe the distance dependence of the SERS enhancement. Using these, we have identified the point at which the characteristic bands for the nucleotides that comprise the oligo disappear from the spectrum. These findings suggest that the applicability of SERS for label-free detection of nucleic acid hybridization is limited to short oligos of less than nine nucleotides.

Probing and mapping electrode surfaces in solid oxide fuel cells.

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen (1-7). The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion(2). Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation(8-12). It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition(8, 10, 13, 14) ("coking") and sulfur poisoning(11, 15) and the manner in which surface modifications stave off this degradation(16). The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated(17-22). In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode.

Application of surface enhanced Raman spectroscopy to the study of SOFC electrode surfaces.

SERS provided by sputtered silver was employed to detect trace amounts of chemical species on SOFC electrodes. Considerable enhancement of Raman signal and lowered detection threshold were shown for coked nickel surfaces, CeO(2) coatings, and cathode materials (LSM and LSCF), suggesting a viable approach to probing electrode degradation and surface catalytic mechanism.

Removal of surface contamination and self-assembled monolayers (SAMs) from silver (Ag) nanorod substrates by plasma cleaning with argon.

Surface contamination of surface-enhanced Raman (SERS)-active metallic substrates has been a limitation to the utility of SERS as an analytical technique, potentially affecting surface coverage, spectral reproducibility, and analytical limits of detection. We have developed a simple and versatile cleaning method for SERS-active Ag nanorod arrays that consists of a short (4 min) exposure of the substrate to an Ar(+) plasma in a low-pressure environment. The findings presented here demonstrate that this cleaning procedure essentially eliminates organic background contamination. This procedure works equally well for self-assembled monolayers of thiolates that strongly adsorb onto Au and Ag surfaces. For SERS-active surfaces composed of arrays of Ag nanorods prepared by oblique-angle vapor deposition, we investigated the (1) Raman band intensities, (2) nanorod morphology via scanning electron microscopy, and (3) surface hydrophobicity via static contact angle measurements, as a function of exposure time of the Ag nanorods to the Ar(+) plasma. Short (4 min) exposure to Ar(+) plasma eliminated background contamination but decreased the observed SERS intensity for re-adsorbed analytes by approximately a factor of 2 while leaving the nanorod morphology essentially unchanged. Prolonged exposure to Ar(+) plasma (>10 min) resulted in substantial morphological changes of the Ag nanorod lattice and led to a decrease in the observed SERS intensities by a factor of 10. The results presented here suggest that Ar(+) plasma cleaning is an efficient process for removing carbonaceous and organic contamination as well as thiolate monolayers from SERS-active Ag surfaces, as long as the plasma conditions and exposure times are carefully monitored.

Surface-enhanced Raman scattering of bacterial cell culture growth media.

The application of surface-enhanced Raman spectroscopy (SERS) to characterizing bacteria is an active area of investigation. Micro- and nano-structured SERS substrates have enabled detection of pathogens present in biofluids. Several publications have focused on determining the spectral bands characteristic of bacteria from different species and cell lines. In this report, the spectra of fifteen commonly used bacterial growth media are presented. In many instances, these spectra are similar to published spectra purportedly characteristic of specific bacterial species. The findings presented herein suggest that bacterial fingerprinting by SERS requires further examination.

Patterned silver nanorod array substrates for surface-enhanced Raman scattering.

A novel method for batch fabrication of substrates for surface-enhanced Raman scattering (SERS) has been developed. A modified platen that fits in a commercial electron beam evaporator enables the simultaneous deposition of Ag nanorod arrays onto six microscope slides by glancing angle deposition. Following removal of substrates from the evaporator, patterned wells are formed by contact printing of a polymer onto the surface. Well dimensions are defined by penetration of the polymer into the nanorod array and subsequent photochemical curing. Inherent advantages of this method include: (1) simultaneous production of several nanorod array substrates with high structural uniformity, (2) physical isolation of nanorod arrays from one another to minimize cross contamination during sample loading, (3) dimensional compatibility of the patterned array with existing SERS microscope, (4) large SERS enhancement afforded by the nanorod array format, (5) small fluid volumes, and (6) ease of use for manual delivery of fluids to each element in the patterned array. In this article, the well-to-well, slide-to-slide, and batch-to-batch variability in physical characteristics and SERS response of substrates prepared via this method is critically examined.

Cyclic square wave voltammetry of single and consecutive reversible electron transfer reactions.

In this report, theory for cyclic square wave voltammetry for single and consecutive reversible electron transfer reactions is presented and experimentally verified. The impact of empirical parameters on the shape of the current-voltage curve is examined. Diagnostic criteria enabling the use of this waveform as a tool for mechanistic analysis of electrode reaction processes are also presented. Since this waveform effectively discriminates against capacitance currents, cyclic square wave voltammetry will enable acquisition of mechanistic information at analyte concentration levels lower than that possible with cyclic voltammetry.

Salt effect on cationic polyacrylamide conformation on mica studied by single molecule "pulling" with scanning probe microscopy.

The effect of salts on adsorbed polyelectrolyte conformations has been studied extensively over the past three decades. Previous researchers have proposed that increasing salt concentration results in larger loops and tails for weak polyelectrolytes adsorbed on a surface. However, no experimental verification of this theory has been published. In this work, we present experimental verification acquired by "pulling" single molecules of a polyelectrolyte from a mica surface using a scanning probe technique. We also present a new method for analyzing changes in adsorbed polymer tail lengths. We demonstrate that increasing solution salt concentration correlates with both loop and tail lengths of an adsorbed low charge density cationic polyacrylamide on a mica substrate.

Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4.

The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100gL(-1) NaCl) and base (3gL(-1) Na2CO3 and 1gL(-1) NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000mgL(-1), the pseudo first-order rate constant (kobs) was 0.029+/-0.006h(-1), corresponding to a half-life of 24.2h and a ZVI surface area-normalized rate constant (kSA) of 2.9x10(-4)Lm(-2)h(-1). However, as the initial dye concentration increased, the kobs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (Vm) of 720+/-88mgL(-1)h(-1) and a half-saturation constant (K) of 1299+/-273mgL(-1). Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2-5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.

Doping of glass with lithium ion.

Doping of glass with lithium ion can be accomplished by exposing the glass to a solution of organic solvent containing a soluble lithium ion salt, such as LiBr and a small amount of water. Under such conditions, the activity of solvated Li+ is very high causing it to partition into the hydrated glass surface. Laser-induced breakdown spectroscopy and atomic absorption spectroscopy have been used to monitor the partitioning between glass and organic phase, respectively.