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Shen Ye

Publications and source records attributed to Shen Ye.

15 recordsLinked to original sources
PubMed2006

Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy.

Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account.

Journal Article↗
PubMed2006

Application of in-situ attenuated total reflection-Fourier transform infrared spectroscopy for the understanding of complex reaction mechanism and kinetics: formic acid oxidation on a Pt film electrode at elevated temperatures.

The potential of in-situ Fourier transform infrared (FTIR) spectroscopy measurements in an attenuated total reflection configuration (ATR-FTIRS) for the evaluation of reaction pathways, elementary reaction steps, and their kinetics is demonstrated for formic acid electrooxidation on a Pt film electrode. Quantitative kinetic information on two elementary steps, formic acid dehydration and CO(ad) oxidation, and on the contributions of the related pathways in the dual path reaction mechanism are derived from IR spectroscopic signals in simultaneous electrochemical and ATR-FTIRS measurements over a wide temperature range (25-80 degrees C). Linearly and multiply bonded CO(ad) and bridge-bonded formate are the only formic acid related stable reaction intermediates detected. With increasing temperature, the steady-state IR signal of CO(ad) increases, while that of formate decreases. Reaction rates for CO(ad) formation via formic acid dehydration and for CO(ad) oxidation as well as the activation energies of these processes were determined at different temperatures, potentials, and surface conditions (with and without preadsorbed CO from formic acid dehydration) from the temporal evolution of the IR intensities of CO(ad) during adsorption/reaction transients, using an IR intensity-CO(ad) coverage calibration. At potentials up to 0.75 V and temperatures from 25 to 80 degrees C, the "indirect" CO pathway contributes less than 5% (at potentials < or =0.6 V significantly below 1%) to the total Faradaic reaction current, making the "direct" pathway by far the dominant one under the present reaction conditions. Much higher activation energies for CO(ad) formation and CO(ad) oxidation compared with the effective activation energy of the total reaction, derived from the Faradaic currents, support this conclusion.

Journal Article↗
PubMed2006

Optical sum-frequency emission from langmuir-blodgett films of variable thickness: effects of the substrate and polar orientation of fatty acids in the films.

The nonlinear optical response arising from a model multilayer structure, i.e., Langmuir-Blodgett (LB) films comprised of different numbers of per-protonated (H) and per-deuterated (D) fatty acid layers on solid substrates, has been evaluated by sum-frequency generation (SFG) spectroscopy. The SFG signals depend significantly on the absolute polar orientation of the fatty acids in the individual layers and on the nonlinear optical response of the substrate. The SFG spectra on gold and fused quartz substrates demonstrate a totally different dependence on the number of the contributing H layers, which it is possible to analyze quantitatively. The results provide important information for understanding the origin of the nonlinear optical responses from ordered systems composed of multiple interfaces and therefore for extracting exact structural information about each interface from the observed SFG signals.

Journal Article↗
PubMed2005

Potential oscillations in galvanostatic electrooxidation of formic acid on platinum: a time-resolved surface-enhanced infrared study.

The mechanism of temporal potential oscillations that occur during galvanostatic formic acid oxidation on a Pt electrode has been investigated by time-resolved surface-enhanced infrared absorption spectroscopy (SEIRAS). Carbon monoxide (CO) and formate were found to adsorb on the surface and change their coverages synchronously with the temporal potential oscillations. Isotopic solution exchange (from H13COOH to H12COOH) and potential step experiments revealed that the oxidation of formic acid proceeds dominantly through adsorbed formate and the decomposition of formate to CO2 is the rate-determining step of the reaction. Adsorbed CO blocks the adsorption of formate and also suppresses the decomposition of formate to CO2, which raises the potential to maintain the applied current. The oxidative removal of CO at a high limiting potential increases the coverage of formate and accelerates the decomposition of formate, resulting in a potential drop and leading to the formation of CO. This cycle repeats itself to give the sustained temporal potential oscillations. The oscillatory dynamics can be explained by using a nonlinear rate equation originally proposed to explain the decomposition of formate and acetate on transition metal surfaces in UHV.

Journal Article↗
PubMed2005

Sum frequency generation from Langmuir-Blodgett multilayer films on metal and dielectric substrates.

Sum frequency generation (SFG) vibrational spectra of cadmium arachidate multilayer films adsorbed on a substrate with high nonresonant susceptibility, i.e., gold, and on a low nonresonant susceptibility substrate, i.e., fused quartz, have been investigated in the C-H stretching region in air. The films were formed by Langmuir-Blodgett (LB) deposition and their spectra recorded using SFG spectrometers employing both 532-nm nanosecond and 800-nm femtosecond lasers, with counter-propagating and co-propagating beam geometries, respectively. Both kinds of substrate were rendered hydrophobic by coating them with per-deuterated octadecanethiol (gold) or per-deuterated cadmium arachidate (fused quartz) monolayers. Single per-protonated arachidate layers in otherwise per-deuterated 10-layer films were used to show that the SFG resonances arise only from the topmost and lowermost layers in a LB film comprised of an even number of per-protonated layers, although the SFG spectra from the two hydrophobic substrates are different from each other. The differences in the spectra from the same ten-layer per-protonated films deposited on the two types of hydrophobic substrate have been explained in terms of a simple model that accounts for resonant and nonresonant contributions.

Adsorption↗
PubMed2005

Hydrogen bonding effects on the surface structure and photoelectrochemical properties of nanostructured SnO2 electrodes modified with porphyrin and fullerene composites.

Hydrogen bonding effects on surface structure, photophysical properties, and photoelectrochemistry have been examined in a mixed film of porphyrin and fullerene composites with and without hydrogen bonding on indium tin oxide and nanostructured SnO2 electrodes. The nanostructured SnO2 electrodes modified with the mixed films of porphyrin and fullerene composites with hydrogen bonding exhibited efficient photocurrent generation compared to the reference systems without hydrogen bonding. Atomic force microscopy, infrared reflection absorption, and ultraviolet-visible absorption spectroscopies and time-resolved fluorescence lifetime and transient absorption spectroscopic measurements disclosed the relationship between the surface structure and photophysical and photoelectrochemical properties relating to the formation of hydrogen bonding between the porphyrins and/or the C60 moieties in the films on the electrode surface. These results show that hydrogen bonding is a highly promising methodology for the fabrication of donor and acceptor composites on nanostructured semiconducting electrodes, which exhibit high photoelectrochemical properties.

Electrochemistry↗
PubMed2005

Oxidation states and CO ligand exchange kinetics in a self-assembled monolayer of a triruthenium cluster studied by in situ infrared spectroscopy.

Oxidation states and CO ligand exchange kinetics in a self-assembled monolayer (SAM) of an oxo-centered triruthenium cluster [Ru(3)(mu3-O)(mu-CH3COO)6(CO)(L1)(L2)] (L1 = [(NC5H4)CH2NHC(O)(CH2)10S-]2, L2 = 4-methylpyridine) have been extensively investigated on the surface of a gold electrode in aqueous and nonaqueous solutions. The SAM exhibits three consecutive one-electron transfers and four oxidation states, which have been characterized by electrochemistry, in situ infrared spectroscopy, and in situ sum frequency generation (SFG) vibrational spectroscopy measurements. The original electron-localized state of the Ru cluster center was changed to electron delocalization states by oxidation or reduction of the central Ru ions. These changes are revealed by the IR absorptions of the CO ligand and the bridging acetate ligands of the triruthenium cluster in the SAM. The IR absorptions of the two kinds of ligands are strongly dependent on the oxidation state of the Ru cluster center. One-electron oxidation of the central Ru ion in the SAM triggers a CO ligand liberation process. Solvent molecules may then occupy the CO site to result in a CO-free SAM. One-electron reduction of this CO-free SAM in a CO-saturated solution leads to re-coordination of the CO ligand into the SAM. Both processes can be precisely controlled by tuning the electrode potential. The kinetics of the CO exchange cycle in the SAM, including liberation and coordination, has been investigated by in situ IR and SFG measurements for the first time. The CO exchange cycle is significantly dependent on the temperature. The reaction rate greatly decreases with decreasing solution temperature, which is an important factor in the CO ligand exchange process. The activation energies of both CO liberation and coordination have been evaluated from the reaction rate constants obtained at various temperatures.

Journal Article↗
PubMed2004

Studying nanoparticle-induced structural changes within fatty acid multilayer films using sum frequency generation vibrational spectroscopy.

The nonlinear optical technique of sum frequency generation (SFG) vibrational spectroscopy has been used for the first time to study CdS nanoparticle/arachidic acid multilayer structures. Using a combination of per-deuterated and per-protonated arachidic acid, it is possible to study individual layers anywhere within the film, buried or on the surface. Before reaction with H2S all layers are highly ordered, but after the reaction the layers become highly disordered, except for the surface layer, which remains well ordered. This sheds new light on the structure and stability of these films and shows that SFG can provide unique structural information.

Cadmium Compounds↗
PubMed2004

Hydrogen bonding on the surface of poly(2-methoxyethyl acrylate).

Hydrogen bonding on the interface and in the bulk of a poly(2-methoxyethyl acrylate) (PMEA) thin film has been investigated by sum frequency generation, infrared reflection absorption, and Raman scattering measurements in different kinds of solutions containing hydrogen-bonding donators. These results indicate that the majority of the carbonyl groups on the PMEA surface are hydrogen-bonded with water or ethanol molecules, while the PMEA bulk is still dominated by the free carbonyl group.

Journal Article↗
PubMed2004

Electrochemical control of CO/NO ligand exchange in a triruthenium cluster monolayer assembled on a gold electrode surface.

A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.

Carbon Monoxide↗
PubMed2004

Quartz crystal microbalance and infrared reflection absorption spectroscopy characterization of bisphenol A absorption in the poly(acrylate) thin films.

The absorption process of bisphenol A (BPA) in a number of poly(acrylate) thin films, such as poly(2-methoxyethyl acrylate) (PMEA), poly(ethyl acrylate) (PEA), poly(n-butyl methacrylate) (PBMA), and poly(methyl methacrylate) (PMMA), has been investigated by quartz crystal microbalance (QCM) and infrared reflection absorption spectroscopy (IRRAS) measurements. Both QCM and IRRAS measurements show that the BPA molecules absorb in PMEA, PEA, and PBMA thin films but not in PMMA thin film. The differences in the BPA absorption behavior are mainly attributed to the difference in the glass transition temperature (T(g)) between these polymers. This absorption behavior also depends on the BPA concentration and polymer film thickness. Furthermore, IRRAS characterization demonstrates that the hydrogen bonding is formed between the hydroxyl group in BPA and the carbonyl group in the poly(acrylate) thin films. BPA molecule absorbed in these polymer thin films can be removed by ethanol rinse treatment. By optimizing experimental conditions for the QCM electrode modified by PMEA thin film, detection limitation of approximately 1 ppb for BPA can be realized by the in situ QCM measurement. This method is expected to be a sensitive in situ detection way for trace BPA in the environmental study.

Journal Article↗
PubMed2004

Cd2+-induced interfacial structural changes of Langmuir-Blodgett films of stearic acid on solid substrates: a sum frequency generation study.

The molecular structures and their stabilities at the outmost-layer of the Langmuir-Blodgett (LB) films of stearic acid on solid substrates have been investigated by a highly surface-sensitive spectroscopic technique, sum frequency generation (SFG), in air and in aqueous solution, using the combination of both normal and deuterated stearic acid. Peaks observed in the SFG spectra are mainly attributed to the terminal methyl group at the outmost layer of the LB films. The SFG spectra in air are virtually identical and are independent of the odd-even property and thickness (1-12) of the LB films, indicating that the even-numbered LB film changes its surface structure after passing through the interface between the water subphase and air, especially when the Cd2+ cation was included in the water subphase. Furthermore, we have demonstrated for the first time using in situ SFG measurement that the interfacial molecular structure at the LB bilayer of stearic acid on the hydrophilic substrates significantly change with immersion in the water subphase containing Cd2+ cation while such a structural change has not been observed in the water subphase without Cd2+. These results clearly indicate that a reorganization process takes place on the surface of the stearic acid bilayer induced by the Cd2+ cation. The electrostatic interaction between the carboxylate headgroup of stearic acid via the Cd2+ cation seems to play an important role in the surface reorganization process both in air and in solution.

Journal Article↗
PubMed2003

Formate, an active intermediate for direct oxidation of methanol on pt electrode.

The electro-oxidation of methanol on a Pt thin film electrode in acidic solution has been investigated by in situ surface-enhanced IR absorption spectroscopy. A new IR peak is observed at around 1320 cm-1 when the electrode potential is more positive than 0.5 V, where the bulk oxidation of MeOH occurs. This peak has been assigned to the symmetric stretching of formate species adsorbed on the Pt electrode surface. It is the first observation of formate adsorption during the electro-oxidation of methanol on a Pt surface. A near proportional relationship between the intensity of the IR band of the formate species and MeOH electro-oxidation current is observed. A new reaction scheme via non-CO pathway with formate as the active intermediate is proposed for the methanol electro-oxidation process.

Journal Article↗