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The successful use of a microband electrode printed on a silicon internal reflection element to perform time resolved infrared spectroscopy is described. Decreasing the critical dimension of the microband electrode to several hundred micrometers provides a sub-microsecond time constant in a Kretschmann configured spectroelectrochemical cell. The high brilliance of synchrotron sourced infrared radiation has been combined with a specially designed horizontal attenuated total reflectance (ATR) microscope to focus the infrared beam on the microband electrode. The first use of a sub-microsecond time constant working electrode for ATR surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) is reported. Measurements show that the advantage afforded by the high brilliance of the synchrotron source is at least partially offset by increased noise from the experimental floor. The test system was the potential induced desorption of an adsorbed monolayer of 4-methoxypyridine (MOP) as measured using step-scan interferometry. Based on diffusion considerations alone, the expected time scale of the process was less than 10 microseconds but was experimentally measured to be three orders of magnitude slower. A defect-mediated dissolution of the condensed film is speculated to be the underlying cause of the unexpected slow kinetics. Key words: ATR-SEIRAS, microband electrode, electrochemical time constant, step-scan interferometry, synchrotron infrared radiation. Nous decrivons l'emploi d'une electrode a microbande imprimee sur un element de reflexion interne en silicium que nous avons appliquee a la spectroscopie infrarouge a resolution temporelle. La reduction de la dimension critique de l'electrode a microbande a quelques centaines de micrometres donne lieu a une constante de temps de l'ordre de l'inframi-croseconde dans une cellule spectroelectrochimique de configuration Kretschmann. La forte brillance du rayonnement synchrotron infrarouge a ete conjuguee a un microscope en reflexion totale attenuee (RTA) horizontal specialement concu pour concentrer le faisceau infrarouge sur l'electrode a microbande. Nous faisons etat de la premiere utilisation d'une electrode de travail a constante de temps dans l'inframicroseconde destinee a la spectroscopie d'absorption infrarouge exaltee de surface en RTA (ATR-SEIRAS ou Attenuated Total Reflectance-Surface Enhanced InfraRed Absorption Spectroscopy). Selon les resultats que nous avons obtenus, l'avantage qu'offre la forte brillance de la source synchrotron est annule, du moins partiellement, par l'augmentation du bruit provenant du plancher de l'environnement experimental. L'eventuelle desorption d'une monocouche de 4methoxypyridine (MOP) adsorbee, mesuree par interferometrie a balayage progressif, constituait le systeme de mise a l'epreuve. Sur la base de considerations centrees uniquement sur la diffusion, le processus aurait du se produire sur une echelle de temps inferieure a 10 microsecondes, mais les mesures experimentales ont revele qu'il etait plus lent de trois ordres de grandeur. Nous posons l'hypothese selon laquelle une dissolution du film condense regie par la presence de defauts pourrait etre la cause sous-jacente de la cinetique etonnamment lente. [Traduit par la Redaction] Mots-cles : ATR-SEIRAS, electrode a microbande, constante de temps electrochimique, interferometrie a balayage progressif, rayonnement synchrotron infrarouge., Introduction The electrochemical RC cell constant, the product of the electrolyte resistance and the capacitance of the working electrode, determines the minimum time required for an electrified interface to respond [...]

The attenuated total reflection-surface-enhanced infrared absorption spectroscopy (SEIRAS) activity of electrodeposited Cu nanoparticles on indium tin oxide-modified Si internal reflection elements is reported. The solution in the cell is easily, and repeatedly, exchanged between a copper deposition bath and a solution containing 4-methoxypyridine through the use of a flow-through spectroelectrochemical cell. 4-methoxypyridine is a convenient SEIRAS probe molecule exhibiting potential-dependent adsorption/desorption on the copper surface. Successive amounts of copper are deposited and then evaluated for electrochemical SEIRAS activity without the need to expose the Cu surface to ambient conditions. It is found that copper deposition charge densities of approximately 60 mC cm−2 exhibit the largest amplitude and most symmetric IR absorption peaks of the investigated electrodeposition conditions. Scanning electron microscopy images of the different Cu charge density films are correlated with the SEIRAS results and establish that close-packed two-dimensional, percolated arrays of oblate, ellipsoidal Cu nanoparticles are responsible for ideal SEIRAS performance and three-dimensional aggregates of larger particles should be avoided. Textured films of Cu nanoparticles are used to determine the adsorbed species present on the copper surface during CO2 electroreduction at low overpotentials. Evidence of adsorbed CO and COH is found at lower overpotentials than those described in previous reports. [ABSTRACT FROM AUTHOR]

The adsorption of arsenic on an amorphous iron oxy(hydroxides) (ferrihydrite) under reductive conditions is reported. The fabrication of an ATR--IR spectroelectrochemical cell that allows the vibrational characterization of arsenate and arsenite adsorbed on a thin film of ferrihydrite is described. The cell is shown to allow the application of reductive conditions through the introduction of a working electrode that is positioned adjacent to the mineral phase. ATR--IR spectra reveal that increasingly negative solution potentials ([E.sub.h]) leads to the loss of adsorbed arsenate prior to the reductive dissolution of Fe(III) in the ferrihydrite. Under the experimental conditions, there is no evidence of reduction of arsenate to arsenite. Through the use of a miniaturized pH probe, the desorption of arsenate through electrochemical biasing is shown to arise solely from competitive adsorption from hydroxide ions produced by electrolysis of water. The results indicate that, within the time frame accessible in these measurements, only extreme reductive conditions are detrimental to arsenic sequestration in mine tailings facilities. Key words: arsenite, arsenate, ferrihydrite, reductive conditions, electrochemistry, ATR--IR. Nous faisons etat de l'adsorption de l'arsenic sur un (oxy)hydroxyde de fer amorphe (ferrihydrite) en conditions reductrices. Nous decrivons la fabrication d'une cellule spectroelectrochimique infrarouge a reflectance totale attenuee (ATR--IR) permettant la caracterisation vibrationnelle de l'arseniate et de l'arsenite adsorbes sur une couche mince de ferrihydrite. Nous avons montre que la cellule permet d'employer des conditions reductrices en y introduisant une electrode de travail placee de maniere adjacente a la phase minerale. Les spectres ATR--IR revelent qu'une augmentation du potentiel de la solution ([E.sub.h]) vers des valeurs de plus en plus negatives entraine une desorption de l'arseniate avant que la dissolution reductrice du Fe(III) present dans le ferrihydrite ne se produise. En conditions experimentales, nous n'observons aucun signe de reduction de l'arseniate en arsenite. A l'aide d'une sonde de pH miniaturisee, nous avons montre que la desorption de l'arseniate par polarisation electrochimique est le resultat direct de l'adsorption competitive d'ions hydroxyde produits par electrolyse de l'eau. Les resultats indiquent que, dans le cadre temporel d'execution de ces mesures, seules des conditions reductrices extremes peuvent nuire a la sequestration de l'arsenic dans les residus d'installations minieres. [Traduit par la Redaction] Mots-cles : arsenite, arseniate, ferrihydrite, conditions reductrices, electrochimie, ATR--IR., Introduction Understanding the process, mechanism, and stability of arsenic sequestration is of critical importance in the design and oversight of wastewater produced by mining activities. Arsenic is highly polymorphic and [...]

Using Schwarzschild objectives, a thin section of a fruit berry seed was chemically imaged with infrared spectromicroscopy, revealing domains of phospholipid rich regions from the cell walls forming the seed's [...]

Micro electro-mechanical systems (MEMS) combining sensing and microfluidics functionalities, as are common in Lab-on-Chip (LoC) devices, are increasingly based on polymers. Benefits of polymers include tunable material properties, the possibility of surface functionalization, compatibility with many micro and nano patterning techniques, and optical transparency. Often, additional materials, such as metals, ceramics, or silicon, are needed for functional or auxiliary purposes, e.g., as electrodes. Hybrid patterning and integration of material composites require an increasing range of fabrication approaches, which must often be newly developed or at least adapted and optimized. Here, a microfabrication process concept is developed that allows one to implement attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and electrochemistry on an LoC device. It is designed to spatially resolve chemical sensitivity and selectivity, which are instrumental for the detection of chemical distributions, e.g., during on-flow chemical and biological reaction chemistry. The processing sequence involves (i) direct-write and soft-contact UV lithography in SUEX dry resist and replication in polydimethylsiloxane (PDMS) elastomers as the fluidic structure; (ii) surface functionalization of PDMS with oxygen plasma, 3-aminopropyl-triethoxysilane (APTES), and a UV-curable glue (NOA 73) for bonding the fluidic structure to the substrate; (iii) double-sided patterning of silicon nitride-coated silicon wafers serving as the ATR-FTIR-active internal reflection element (IRE) on one side and the electrode-covered substrate for microfluidics on the back side with lift-off and sputter-based patterning of gold electrodes; and (iv) a custom-designed active vacuum positioning and alignment setup. Fluidic channels of 100 μm height and 600 μm width in 5 mm thick PDMS were fabricated on 2" and 4" demonstrators. Electrochemistry on-chip functionality was demonstrated by cyclic voltammetry (CV) of redox reactions involving iron cyanides in different oxidation states. Further, ATR-FTIR measurements of laminar co-flows of H2O and D2O demonstrated the chemical mapping capabilities of the modular fabrication concept of the LoC devices. [ABSTRACT FROM AUTHOR]

The surface stress response of micromechanical cantilever-based sensors was studied as a function of the morphology, adhesion, and cleanliness of the gold sensing surface. Two model systems were investigated: the adsorption of alkanethiol self-assembled monolayers at the gas--solid interface and the potential-controlled adsorption of anions at the liquid--solid interface. The potential-induced surface stress, on a smooth and continuous polycrystalline Au(111)-textured microcantilever in 0.1 M HCl[O.sub.4], is in excellent agreement with macroscopic Au(111) single-crystal electrode results. It is shown that ambient contaminants on the sensing surface dramatically alter the surface stress-potential response. This observation can be misinterpreted as evidence that for polycrystalline Au(111) microcantilever electrodes, surface stress is dominated by surface energy change. Results for anions adsorption on gold are in contrast to the gas-phase model system. We demonstrate that the average grain size of the gold sensing surface strongly influences the magnitude of the surface stress change induced by the adsorption of octanethiol. A 25-fold amplification of the change in surface stress is observed on increasing the average gold grain size of the sensing surface from 90 to 500 nm.

Palladium nanoparticles have been electrodeposited on the surfaces of conductive indium tin oxide (ITO) modified silicon internal reflection elements. The resulting films are shown to be excellent platforms for attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) studies of palladium surfaces. Monitoring the mid-infrared reflectivity of the interface during the constant potential electrodepostion of a Pd2+ precursor reveals a distinct and reproducible minimum that corresponds to the onset of the electronic percolation threshold of the deposited metal islands as confirmed by scanning electron microscopy. Effective medium theory (EMT) is used to model the reflectivity of the Si/ITO/Pd interface as a function of the volume fraction of the deposited metal and to calculate the ATR-SEIRA spectra of an adsorbed monolayer of organic molecules. EMT calculations are in qualitative agreement with most aspects of the experimental spectra which show that the intensities and spectral line shapes are highly dependent on the amount of deposited palladium. The methodology is applied to the potential dependent adsorption of 4-methoxypyridine on palladium. The experimental results show that the pyridine derivative adopts an edge-tilted orientation on oxide covered Pd and undergoes an orientation change in the hydrogen adsorption region that increases both the degree of edge-tilt and the extent of π-bonding between the pyridine ring and the metal. [ABSTRACT FROM AUTHOR]

We show that a microgrooved ATR-SEIRAS optimized Si ATR wafer designed to allow high angles of incidence at the electrode-solution interface provides improved signal-to-noise in electrochemical ATR-SEIRAS. Microgrooved Si ATR [...]

The synthesis and structural characterization of aluminum- and gallium-bridged [1.1]chromarenophanes and [1.1]molybdarenophanes are reported. These compounds are shown to contain two pairs of inner [alpha] protons that are oriented toward each other.

We monitor potential-induced changes at a Au film electrode using the ATR-SEIRAS sampling technique. Benefits are discussed. Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) provides in situ surface-sensitive IR [...]