Boon Siang Yeo

Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed.

Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals

Stable and selective electrochemical reduction of carbon dioxide to ethylene was achieved using copper mesocrystal catalysts in 0.1 M KHCO3. The Cu mesocrystal catalysts were facilely derived by the in situ reduction of a thin CuCl film during the first 200 seconds of the CO2 electroreduction process. At −0.99 V vs. RHE, the Faradaic efficiency of ethylene formation using these Cu mesocrystals was ~18× larger than that of methane and forms up to 81% of the total carbonaceous products. Control CO2 reduction experiments show that this selectivity towards C2H4 formation could not be replicated by using regular copper nanoparticles formed by pulse electrodeposition. High resolution transmission electron microscopy reveals the presence of both (100)Cu facets and atomic steps in the Cu mesocrystals which we assign as active sites in catalyzing the reduction of CO2 to C2H4. CO adsorption measurements suggest that the remarkable C2H4 selectivity could be attributed to the greater propensity of CO adsorption on Cu mesocrystals than on other types of Cu surfaces. The Cu mesocrystals remained active and selective towards C2H4 formation for longer than six hours. This is an important and industrially relevant feature missing from many reported Cu-based CO2 reduction catalysts.

Towards chemical analysis of nanostructures in biofilms II: tip-enhanced Raman spectroscopy of alginates

AbstractThis study examines the feasibility of using tip-enhanced Raman spectroscopy (TERS) for label-free chemical characterization of nanostructures in biological systems. For this purpose, a well-defined model system consisting of calcium alginate fibers is studied. In a companion paper, calcium alginate fibers and their network structures were shown to be a good model for the extracellular polysaccharides of biofilms at the nanoscale. TERS analysis of biological macromolecules, such as alginates, is complicated by heterogeneity in their sequence, molecular weight, and conformations, their small Raman cross-section, and the large number of functional groups, which can chemically interact with the silver surface of the tip and cause significant band shifts. Due to these effects, Raman frequencies in TERS spectra of biopolymers do not necessarily resemble band positions in the normal Raman spectrum of the bulk material, as is the case for less complex samples (e.g., dye molecules) studied so far. Additionally, analyte decomposition due to laser heating can have a significant influence, and carbon contamination signals can sometimes even overwhelm the weak analyte signals. Based on the investigation of alginates, strategies for spectra correction, choice of appropriate reference samples, and data interpretation are presented. With this approach, characteristic frequency ranges and specific marker bands can be found for biological macromolecules that can be employed for their identification in complex environments. FigureTERS spectrum of a calcium alginate fiber bundle

Surface multiheme c-type cytochromes from Thermincola potens and implications for respiratory metal reduction by Gram-positive bacteria

Almost nothing is known about the mechanisms of dissimilatory metal reduction by Gram-positive bacteria, although they may be the dominant species in some environments. Thermincola potens strain JR was isolated from the anode of a microbial fuel cell inoculated with anaerobic digester sludge and operated at 55 °C. Preliminary characterization revealed that T. potens coupled acetate oxidation to the reduction of hydrous ferric oxides (HFO) or anthraquinone-2,6-disulfonate (AQDS), an analog of the redox active components of humic substances. The genome of T. potens was recently sequenced, and the abundance of multiheme c-type cytochromes (MHCs) is unusual for a Gram-positive bacterium. We present evidence from trypsin-shaving LC-MS/MS experiments and surface-enhanced Raman spectroscopy (SERS) that indicates the expression of a number of MHCs during T. potens growth on either HFO or AQDS, and that several MHCs are localized to the cell wall or cell surface. Furthermore, one of the MHCs can be extracted from cells with low pH or denaturants, suggesting a loose association with the cell wall or cell surface. Electron microscopy does not reveal an S-layer, and the precipitation of silver metal on the cell surface is inhibited by cyanide, supporting the involvement of surface-localized redox-active heme proteins in dissimilatory metal reduction. These results provide unique direct evidence for cell wall-associated cytochromes and support MHC involvement in conducting electrons across the cell envelope of a Gram-positive bacterium.

Enhancement of Raman Signals with Silver-Coated Tips

Silver coated SiN and SiO2 tips have been fabricated for use with a bottom-illumination tip-enhanced Raman spectroscopy (TERS) setup with a 488 nm laser excitation. SiN tips with 50–60 nm of deposited Ag give the best TERS enhancements for brilliant cresyl blue test analyte spin-coated on a glass slide. Ag nanoparticles on SiN or SiO2 rather than Si tips are better for TERS because of the proximity of the wavelengths of their surface plasmon resonance to 488 nm. Adjustments of tilt angle of the metallized tip with respect to the surface plane is shown to considerably raise the intensities of the TERS signals, even from tips that initially appear to be rather non-enhancing. This work helps to enable the more frequent use of the 488 nm laser for nanoscale chemical analysis with both TERS and fluorescence imaging in the same setup.

Nanoscale probing of a polymer-blend thin film with tip-enhanced Raman spectroscopy.

Fundamental advances have been made in the spatially resolved chemical analysis of polymer thin films. Tip-enhanced Raman spectroscopy (TERS) is used to investigate the surface composition of a mixed polyisoprene (PI) and polystyrene (PS) thin film. High-quality TER spectra are collected from these nonresonant Raman-active polymers. A wealth of structural information is obtained, some of which cannot be acquired with conventional analytical techniques. PI and PS are identified at the surface and subsurface, respectively. Differences in the band intensities suggest strongly that the polymer layers are not uniformly thick, and that nanopores are present under the film surface. The continuous PS subsurface layer and subsurface nanopores have hitherto not been identified. These data are obtained with nanometer spatial resolution. Confocal far-field Raman spectroscopy and X-ray photoelectron spectroscopy are employed to corroborate some of the results. With routine production of highly enhancing TERS tips expected in the near future, it is predicted that TERS will be of great use for the rigorous chemical analysis of polymer and other composite systems with nanometer spatial resolution.

Identification of hydroperoxy species as reaction intermediates in the electrochemical evolution of oxygen on gold.

Efficient electrochemical splitting of H2 Ot o O 2 and H2 fuels has become an important goal in the quest for a renewable source of energy. [1] A major source of the inefficiency of this process is the significant overpotential associated with the anodic oxygen evolution reaction (OER). Understanding the mechanism of the OER could help in identifying the elementary processes contributing to OER overpotential and their relationship to the anode composition and morphology. While the OER has been investigated both experimentally and theoretically for over 50 years, its mechanism and the identity of the chemical intermediates involved remain uncertain. [2–7] Two principal pathways have been postulated for the OER on metal surfaces, such as gold (Au). The first involves a direct recombination of oxygen atoms to give O2, as shown in Equations (1)–(4):

On the chemical state of Co oxide electrocatalysts during alkaline water splitting

Resonant inelastic X-ray scattering and high-resolution X-ray absorption spectroscopy were used to identify the chemical state of a Co electrocatalyst in situ during the oxygen evolution reaction. After anodic electrodeposition onto Au(111) from a Co(2+)-containing electrolyte, the chemical environment of Co can be identified to be almost identical to CoOOH. With increasing potentials, a subtle increase of the Co oxidation state is observed, indicating a non-stoichiometric composition of the working OER catalyst containing a small fraction of Co(4+) sites. In order to confirm this interpretation, we used density functional theory with a Hubbard-U correction approach to compute X-ray absorption spectra of model compounds, which agree well with the experimental spectra. In situ monitoring of catalyst local structure and bonding is essential in the development of structure-activity relationships that can guide the discovery of efficient and earth abundant water splitting catalysts.

Tuning the resonance frequency of Ag-coated dielectric tips

A finite element model was built to investigate how to optimize localized plasmon resonances of an Ag-coated dielectric tip for tip-enhanced Raman spectroscopy (TERS). The relation between the resonance frequency, the electric field enhancement and the optical constant of the dielectric tip was numerically investigated. The results show that increasing the refractive index of the dielectric tip can significantly red shift the localized plasmon modes excited on the Ag-coated dielectric tip, and consequently alter the field enhancement. Moreover, the influence of the width of the resonance on the Raman enhancement was also considered. When taking all the factors into account, we find that an Ag-coated low-refractive index dielectric tip provides the best Raman enhancement in the blue-green spectral range. This is consistent with our prior experimental results.

Multifunctional microscope for far-field and tip-enhanced Raman spectroscopy

The development of a versatile and easy-to-use instrument designed for Raman micro- and nanospectroscopy in the visible range is described in this work. An atomic force microscope, an inverted confocal microscope, and a piezostage are combined to perform an accurate and fast tip-laser alignment and to characterize large areas under the same conditions of illumination across the surface. In addition, a metallized tip is used to locally enhance the electromagnetic field and to probe the sample surface leading to in situ chemical analysis at the nanoscale. Both far-field and tip-enhanced Raman spectroscopies (TERS) have been carried out on dye molecules and on nano-objects with short exposure times. The TERS observation of tip-induced sample deformation on single-walled carbon nanotubes is also presented.