Biomedical subjects

Daniel A Scherson

Publications and source records attributed to Daniel A Scherson.

18 recordsLinked to original sources

PubMed2007

Simultaneous in situ reflectance and probe beam deflection measurements at solid electrode-aqueous electrolyte interfaces.

A method is herein described for performing simultaneous in situ normal incidence reflectance spectroscopy (DeltaR/R, lambda = 633 nm) and probe beam deflection (PBD) measurements at solid electrodes in aqueous electrolytes, while scanning the potential linearly between two prescribed limits. Results obtained for Au in 0.1 M HClO4 and for Pt in both 0.1 M HClO4 and 0.1 M NaOH were found to be in excellent agreement with those reported in the literature for each individual spectroelectrochemical technique under otherwise similar conditions. Data collected for Pt electrodes in CO-saturated 0.1 M HClO4 revealed rather sudden changes in both DeltaR/R and PBD signals in the voltammetric region where the characteristic sharp peak associated with the oxidation of adsorbed CO occurs. This behavior was ascribed, respectively, to oxide formation (DeltaR/R) and to changes in the electrolyte composition in region neighboring the electrode, involving predominantly the acid concentration (PBD). In contrast, CO oxidation on Pt in 0.1 M NaOH yielded a PBD response consistent with formation of solution-phase carbonate via the reaction of the product, CO2, with hydroxyl ion. The exquisite sensitivity of DeltaR/R and PBD to interfacial phenomena was further illustrated using a monolayer of hemin irreversibly adsorbed on glassy carbon surfaces in 0.1 M Na2B4O7 (pH approximately 9.2). For this system, DeltaR/R was found to be proportional to the relative fractions of hemin and its reduced counterpart, while the PBD signal could be correlated with corresponding variations in the electrolyte concentration induced by the surface-bound redox process.

Journal Article↗

PubMed2006

In situ, time-resolved reflectance spectroscopy in the microsecond domain: oxidation of adsorbed carbon monoxide on polycrystalline pt microelectrodes in aqueous solutions.

The dynamics of the electrooxidation of adsorbed CO, COads, on polycrystalline Pt microelectrodes has been examined in CO-saturated 0.5 M H2SO4 and 0.5 M HClO4 aqueous solutions, using in situ, time-resolved, normalized differential reflectance spectroscopy lambda = 633 nm). Attention was focused on the unique dependence of COads oxidation on the potential at which the adsorbed full CO monolayer is assembled (i.e., hydrogen adsorption/desorption vs the double-layer region) using both fast linear scan voltammetry and potential step techniques. As evidenced from the data collected, COads oxidation at a fixed potential proceeds at slower rates when the monolayer is formed in the double- layer region compared to when it is formed in the hydrogen adsorption/desorption region. Possible explanations for this effect are discussed.

Adsorption↗

PubMed2006

Oxidation of adsorbed CO on Pt(111) in CO-saturated perchloric acid aqueous solutions: simultaneous in situ time-resolved reflectance spectroscopy and second harmonic generation studies.

Simultaneous normalized differential reflectance spectroscopy (DeltaR/R) and second harmonic generation (SHG) has been employed to follow, independently, OH and adsorbed CO (CO(ads)) on a single Pt(111) microfacet in CO-saturated aqueous perchloric acidic solutions during voltammetric cycles, leading to the oxidation of CO(ads) and subsequent readsorption of CO on the surface. The results obtained are consistent with the disruption of the radical19 x radical19R19.1 degrees phase just prior to the oxidation of adsorbed CO.

Letter↗

PubMed2006

Assembly and electrochemical characterization of nanometer-scale electrode|solid electrolyte interfaces.

A technique is herein described for the assembly and characterization of nanometer-scale metal electrode|solid electrolyte interfaces of variable dimensions. The specific system examined in this work involves a sharp Pt tip attached to the piezo-driven head of a scanning tunneling microscope (STM) allowing the tip to be inserted into (or retrieved from) a Nafion membrane placed normal to the direction of tip travel. The actual Pt|Nafion area of contact was determined by coulometric analysis of the characteristic voltammetric features of Pt, using the tip as the working electrode and a much larger Pt gauze attached to the other side of the Nafion as a counter-reference electrode, yielding for some of the interfaces examined values equivalent to as low as 35 000 Pt surface atoms. This rather versatile arrangement allows experiments to be performed in both inert (Ar) and reactive atmospheres, such as oxygen or hydrogen on either or both sides of the membrane, under controlled humidity conditions, and thus sheds light into such phenomena as changes in the overall faradaic currents induced by plastic deformations of the Nafion as well as fundamental aspects of mass transport at reactant gas|Pt|Nafion three-boundary interfaces of relevance to polymer electrolyte fuel cells (PEFCs).

Journal Article↗

PubMed2005

Hydration of CO adsorbed on Pt(100) at cryogenic temperatures in UHV environments.

Adsorption of small amounts of D(2)O (ca. 0.01 L exposure) on CO(sat)/Pt(100) surfaces in ultrahigh vacuum at 105 K was found to split the asymmetric peak at 2100 cm(-1) in the infrared reflection absorption spectra attributed to the stretching of CO adsorbed on atop sites into two clearly defined features: an intense component, which shifted toward lower energies due to surface hydration of adsorbed CO (originally at 2100 cm(-1), peak a), and a smaller peak centered at 2094 cm(-1) (peak b), which remained fixed in position even after closing the D(2)O dosing valve. The energies of peaks a and b, as determined by statistical analyses, correlated very well with those reported in the literature for CO adsorbed at high coverages on Pt(100) originally in the (5 x 20) or (hex) reconstruction, and on the unreconstructed Pt(100)-(1 x 1), respectively, at 90 K. On these bases, the asymmetry of the peak observed for CO(sat)/Pt(100) (no D(2)O dosing) is ascribed to the presence of CO linearly adsorbed on these two different sites on the surface, for which the rate of hydration is larger for the (5 x 20) compared to the (1 x 1) phases.

Letter↗

PubMed2005

Optical determination of differential coverage-potential relations of redox-active species immobilized on electrode surfaces.

Single-wavelength (HeNe laser, lambda = 633 nm), normal incidence UV-visible reflectance spectroscopy was used to monitor the optical properties of the glassy carbon (GC)|0.2 M NaOH(aq) interface as a function of the applied potential, E. Whereas the electroreflectance coefficient for bare GC was found to be small and potential independent, surface functionalization by an irreversibly adsorbed layer of tetrasulfonated cobalt phthalocyanine (CoTSPc) yielded a clearly defined sigmoidally shaped normalized reflectance change (DeltaR/R) vs E curve over the potential region in which the adsorbate displayed redox peaks. Assuming DeltaR/R is proportional to the extent of redox conversion, as has been reported for macrocycles adsorbed on other types of carbon (e.g., Kim, S.; Xu, X.; Bae, I. T.; Wang, Z.; Scherson, D. A. Anal. Chem. 1990, 62, 2647-2650), differential coverage-potential relations were determined based purely on the optical data collected. A similar optical behavior was found for irreversible adsorbed CoPc and tetraamino CoPc (CoTAPc) adsorbed on GC, for which the voltammetric peaks were ill-defined, too small for coulometric analyses to be reliably performed, or both. No detectable changes in the DeltaR/R vs E profiles of either bare or macrocyclic-functionalized surfaces were observed upon addition of hydrazine to the neat 0.2 M NaOH solution at potentials at which these surfaces display electrocatalytic properties for its oxidation. Possible factors responsible for this behavior are discussed.

Journal Article↗

PubMed2005

Electrochemistry in ultrahigh vacuum: underpotential deposition of Al on polycrystalline W and Au from room temperature AlCl(3)/1-ethyl-3-methylimidazolium chloride melts.

The voltammetric characteristics of polycrystalline Au and W electrodes cleaned (thermal annealing at 1100 K) and characterized (Auger electron spectroscopy) in ultrahigh vacuum (UHV) have been examined in ultrapure AlCl(3)/1-ethyl-3-methylimidazolium chloride (EtMeImCl) melts in UHV. These experiments were performed using a custom-designed transfer system that allows for the all-Al electrochemical cell to be filled with EtMeImCl in an auxiliary UHV chamber and later transferred under UHV to the main UHV chamber that houses the Auger electron spectrometer. The results obtained for the underpotential (UPD) and bulk deposition of Al on Au were found to be very similar to those reported in the literature for measurements carried out under 1 atm of an inert gas in a glovebox. For the far more reactive W surfaces, voltammetric features ascribed to the stripping of underpotential-deposited Al could be observed following a single scan from 1.0 V vs Al(3+)/Al to a potential negative enough for bulk deposition of Al to ensue. This behavior is unlike that reported in the literature for experiments performed in a glovebox, which required either extensive potential cycling in the Al bulk deposition and stripping region or excursions to potentials positive enough for chlorine evolution to ensue for Al UPD features to be clearly discerned. These observations open new prospects for fundamental electrochemical studies of well-characterized, highly reactive metals, including single crystals, in a variety of low vapor pressure ionic liquids.

Journal Article↗

PubMed2005

Surface dynamics of coadsorbed CO and D2O on Pt(100) in ultrahigh vacuum as studied by time-resolved infrared reflection absorption spectroscopy.

Changes in the properties of CO adsorbed at saturation coverages on Pt(100) induced by subsequent coadsorption of fixed amounts of D2O at 105 K in ultrahigh vacuum (UHV) were monitored by time-resolved infrared reflection absorption spectroscopy (tr-IRAS). The linear- and bridge-bonded CO stretching features were found to change in intensity and shift toward lower energies as a function of time at fixed CO and D2O coverages. Also observed was the development of multiple features in both CO spectral regions depending on the amount of D2O on the surface. These findings indicate that, under the conditions of these experiments, the interfacial dynamics are relatively slow, on the order of minutes, involving a gradual rearrangement of adsorbed CO and D2O on the surface to yield surface solvated CO, as has been suggested in the literature (Kizhakevariam et al. J. Chem. Phys. 1994, 100, 6750). This factor should be considered when comparing, quantitatively, shifts induced by water coadsorption with CO on Pt single crystals in UHV with CO adsorption on the same surfaces in electrochemical environments.

Letter↗

PubMed2005

Carbon monoxide adsorption on Ru-modified Pt surfaces: time-resolved infrared reflection absorption studies in ultrahigh vacuum.

The vibrational spectra of CO adsorbed on Ru-modified Pt(100) surfaces prepared by chemical vapor deposition (condensation of Ru(3)(CO)(12) at 105 K followed by X-ray irradiation and thermal decomposition at 650 K in ultrahigh vacuum, UHV) was investigated by time-resolved infrared reflection absorption spectroscopy (IRAS) in UHV. Spectra were recorded while Ru/Pt(100) bimetallic surfaces (theta(Ru) = 0.24 and 0.52 by X-ray photoelectron spectroscopy, XPS) were dosed with gas-phase CO. Analysis of the data revealed that for a wide range of calibrated CO exposures, the linear CO-stretching region displays two features: a higher energy peak (2085-2100 cm(-1)), attributed to CO adsorbed on pristine Pt(100) sites, and a lower energy peak (2066-2092 cm(-1)), ascribed to adsorption of CO on sites on the surface induced by the presence of Ru. Similar experiments were performed on bimetallic specimens annealed repeatedly in UHV to 650 K to promote partial Ru dissolution into the lattice and thus render surfaces gradually enriched in Pt. For all surfaces and CO exposures examined, the total integrated area under the two CO spectral features remained fairly constant and equal in value to the corresponding areas found for bare Pt(100). If it is assumed that a fixed exposure leads to a fixed coverage on both bare and Ru-modified Pt(100)surfaces, and the thermal treatment leads to an exchange of Ru by Pt sites without altering significantly the total number of metal sites on the surface, the absorption cross sections for both of these peaks are virtually the same.

Journal Article↗

PubMed2005

Metal-ion adsorption on carboxyl-bearing self-assembled monolayers covalently bound to magnetic nanoparticles.

Hematite nanoparticles have been functionalized with a self-assembled monolayer of undecanoic acid (UA) by covalent attachment via siloxane groups. The number density of carboxylic/carboxylate groups on the surface was determined by titration, yielding values on the order of 10(14) UA molecules/cm(2) and thus consistent with a closed-packed monolayer. The ability of these functionalized particles to adsorb Cd(2+) in the ppm range was demonstrated using in situ anodic stripping voltammetry.

Adsorption↗

PubMed2005

In situ, time-resolved normal incidence reflectance spectroscopy of polycrystalline platinum microelectrodes in aqueous electrolytes.

In situ normal incidence reflectance spectra of polycrystalline Pt microelectrodes have been monitored as a function of the applied potential in aqueous 0.5 M H(2)SO(4) using a He-Ne laser source (633 nm) and a beam splitter/microscope objective arrangement. Data recorded during voltammetric cycles in Ar-purged solutions revealed a linear correlation between the normalized change in reflectance, DeltaR/R = (R(s) - R(ref))/R(ref) (where R(s) and R(ref) are the light intensities measured by the detector at the sampling, s, and reference potentials, ref, respectively), and the extent of oxidation of the Pt surface over a wide coverage range. Reflectance spectra were also collected in CO-saturated 0.5 M H(2)SO(4) during chronocoulometric measurements involving judiciously selected limits for both the potential step and duty cycle parameters. Analysis of these results made it possible to extract contributions to the current derived from oxide formation during oxidation of adsorbed and bulk CO, based strictly on the optical response.

Adsorption↗

PubMed2004

In situ dual-beam coincidence second harmonic generation as a probe of spatially resolved dynamics at electrochemical interfaces.

In situ dual-beam coincidence second harmonic generation was used to monitor spatially resolved dynamics at the Pt(111)/CO-saturated 0.1 M HClO4 interface. The results obtained showed that, for potential steps from 30 to about 870 mV vs RHE, the full electrooxidation of CO as evidenced from SHG occurred at different times for the two areas of the Pt(111) surface probed by the beams. On this basis, the diffusional rates of adsorbed CO cannot be assumed to be generally large enough as to render the entire surface in a homogeneous state, as invoked by the mean field approximation model.

Journal Article↗

PubMed2004

Binding of Cd2+ to self-assembled bilayers bearing pyridine terminal groups: attenuated total reflection Fourier transform infrared spectroscopic studies.

Various aspects of the adsorption of Cd2+ on self-assembled monolayers (SAMs) of 4-heptadecylpyridine (HDpy) and 7-tridecyl-4-methyl-1,10-bipyridine (TMbipy) supported on an octadecylsilane (ODS)-modified Ge prism have been examined both ex situ (dry) and in situ (in the presence of aqueous solutions) using attenuated total reflection Fourier transform infrared spectroscopy. In direct analogy with the behavior found for a variety of genuine pyridine (py) and bipyridine (bipy) metal ion complexes, Cd2+ binding to both SAMs led to shifts in the skeletal vibrational modes of the corresponding uncoordinated ligands in the region 1650-1400 cm(-1), toward higher energies. Analysis of spectra acquired ex situ for HDpy/ODS/Ge and TMbipy/ODS/Ge before and after exposure to 0.1 mM [Cd2+] yielded values for the fraction of uncoordinated py, theta(py(un)), and uncoordinated bipy, theta(bipy(un)), of about 0.5 and about 0.1, respectively. The features attributed to the py(un) groups for spectra collected for HDpy/ODS/Ge in situ and ex situ were found to be virtually identical, making it possible to isolate by graphical means the most prominent band of py(co) centered at about 1615 cm(-l) for HDpy/ODS/Ge collected in situ. The resulting bands for pure py(co) and pyun in situ were then used to deconvolute spectra recorded in situ for HPpy/ODS/Ge in contact with Cd2+containing solutions in the range 10 nM < [Cd2+] < 0.1 mM, from which information regarding the adsorption isotherm was obtained.

Journal Article↗

PubMed2004

Diffusion boundary layer of a rotating disk electrode as a thin-layer spectroelectrochemical cell.

A UV-visible rapid scan spectrophotometer (RSS) was coupled to a Au rotating disk electrode (RDE) for monitoring at near-normal incidence the reflection-absorption spectrum of the diffusion boundary layer in [Fe(CN)(6)](4)(-) aqueous solutions over a potential region in which [Fe(CN)(6)](4-) oxidizes, generating highly absorbing [Fe(CN)(6)](3-) (lambda(max) = 420 nm). Measurements were performed under steady-state conditions at rotation rates, omega, in the range 300 <or= omega <or= 2500 rpm, yielding well-defined spectra displaying characteristic features of [Fe(CN)(6)](3-). In agreement with theoretical predictions, the absorbance A at lambda(max), using as a reference A(lambda(max)) for the spectrum recorded at a potential negative to the onset of [Fe(CN)(6)](4-) oxidation, was found to be proportional both to the current and also to omega(1/2) under conditions in which E was positive enough for the reaction to proceed under diffusion-limited control.

Journal Article↗

PubMed2004

Self-assembled monolayers of 4-mercaptopyridine on Au(111): a potential-induced phase transition in sulfuric acid solutions.

In situ scanning tunneling microscopy images of self-assembled monolayers (SAMs) of 4-mercaptopyridine (4-MPy) on Au(111) recorded in neat 0.1 M H2SO4 solutions provided evidence for a potential-induced phase transition over the range 0.40-0.15 V versus saturated calomel electrode. Analysis of the data was consistent with the presence of a (5 x square root(3)) and (10 x square root(3)) superstructure (phase A) at the positive end, that is, 0.40 V, for which the local coverage, theta(loc), is about 0.2 (two 4-MPy molecules per unit cell), which compresses at the negative end, that is, 0.15 V, to yield a much denser superstructure (phase B, theta(loc) ca. 0.5). This behavior is unlike that reported for the 4-MPy-Au(111) SAM prepared by identical means, in 0.1 M HClO4 (or in sulfate solutions of a much higher pH) for which only the (5 x square root(3)) superstructure was observed over the same potential range. The compression associated with the phase A to phase B transition is attributed to the formation of a hydrogen-bonded network of bisulfate coordinated in turn to the 4-MPy layer via the acidic hydrogens of the pyridinium moieties. Such conditions promote better packing of adsorbed 4-MPy species, which are aided by intermolecular pi-pi ring interactions, resulting in higher local coverages.

Gold↗

PubMed2003

In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte.

Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.

Journal Article↗

PubMed2003

Dynamics of a surface phase transition as monitored by in situ second harmonic generation.

The dynamics of the (2 x 2)-3CO <--> dilute phase transition involving CO adsorbed on Pt(111) microfacets has been monitored in situ in a CO-saturated acidic electrolyte using potential step-second harmonic generation techniques. Apparent time constants derived strictly from the optical data were found to be orders of magnitude slower for the forward process as compared to those of the reverse process. This behavior is consistent with the activated nature of CO electrooxidation, which requires the presence of a neighboring adsorbed oxygenated species, for example, hydroxyl, for the process to ensue.

Journal Article↗

PubMed2002

The electrochemical oxidation of carbon monoxide adsorbed on Pt(111) in aqueous electrolytes as monitored by in situ potential step-second harmonic generation.

The dynamics of electrooxidation of adsorbed CO on Pt(111) microfacets was examined in CO-saturated 0.1 M HClO4 aqueous solutions by in situ time resolved second harmonic generation (SHG). Analysis of the temporal dependence of the intensity of the SHG signals recorded for experiments in which the potential was stepped to values high enough for adsorbed CO oxidation to ensue, was found to be consistent with the mean field theory model, yielding rate constants somewhat higher than those reported by Lebedeva et al. (N. P. Lebedeva, M. T. M. Koper, J. M. Feliu and R. A. v. Santen, J. Electroanal. Chem., 2002, 524-525, 242-251) in sulfuric acid solutions. The smaller rates observed by these authors may be ascribed to the presence of anions, ie. in all likelihood bisulfate, which are capable of competing effectively for Pt sites thereby blocking formation of oxygenated species on the surface. Also discussed in this work are the virtues and limitations of in situ SHG for monitoring fast surface processes.

Journal Article↗