Naoya Nishi

Chain-length-dependent change in the structure of self-assembled monolayers of n-alkanethiols on Au(111) probed by broad-bandwidth sum frequency generation spectroscopy

The structure of the self-assembled monolayers (SAMs) of n-alkanethiols [CH3(CH2)nSH, n=3–11, 13–15, 17] on Au(111) has been studied using broad-bandwidth sum frequency generation spectroscopy. Sum-frequency vibrational spectra show three pronounced CH3 vibrational modes for all alkanethiol investigated, indicating that the commonly accepted picture that the alkyl chain for the long-chain alkanethiol SAMs has the all-trans conformation applies even to the short chain SAMs. The chain-length dependence of the ratio of the intensity for the CH3 symmetric vibrational mode to that for the CH3 asymmetric mode clearly shows the odd–even effect due to the difference in the direction of methyl group for SAMs with odd and even n, also supporting that the alkyl chain of SAMs has the all-trans conformation. An analysis of the vibrational intensities with respect to the angle between the main axis of the methyl group and the surface normal reveals that the structure of the alkanethiol SAMs gradually changes with n.

Oxygen chemical potential variation in ceria-based solid oxide fuel cells determined by Raman spectroscopy

The profile of oxygen chemical potential in 20 mol% Sm-doped ceria Ce0.8Sm0.2O2−δ (SDC) at 1273 K under the open-circuit conditions of solid oxide fuel cells was determined using Raman spectroscopy. SDC pellets were annealed in various atmospheres, and a peak intensity of a Raman band of SDC in the range 540–600 cm−1, which has been assigned to a band that originates in the oxygen vacancies, increased with decreasing oxygen partial pressure [P(O2)] upon annealing. A clear relationship between the peak area of the oxygen-vacancy band and P(O2) upon annealing was obtained. This relationship was used to determine the profile of oxygen partial pressure, P(O2), in SDC located between fuel and air. The experimental profile was in good agreement with that obtained theoretically. The profile revealed that most part of SDC was mixed conductive and only a thin layer adjacent to the air side remained purely ionic conductive under the open-circuit conditions of SOFCs.

Ionic multilayers at the free surface of an ionic liquid, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, probed by x-ray reflectivity measurements.

The presence of ionic multilayers at the free surface of an ionic liquid, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide ([TOMA(+)][C(4)C(4)N(-)]), extending into the bulk from the surface to the depth of approximately 60 A has been probed by x-ray reflectivity measurements. The reflectivity versus momentum transfer (Q) plot shows a broad peak at Q approximately 0.4 A(-1), implying the presence of ionic layers at the [TOMA(+)][C(4)C(4)N(-)] surface. The analysis using model fittings revealed that at least four layers are formed with the interlayer distance of 16 A. TOMA(+) and C(4)C(4)N(-) are suggested not to be segregated as alternating cationic and anionic layers at the [TOMA(+)][C(4)C(4)N(-)] surface. It is likely that the detection of the ionic multilayers with x-ray reflectivity has been realized by virtue of the greater size of TOMA(+) and C(4)C(4)N(-) and the high critical temperature of [TOMA(+)][C(4)C(4)N(-)].

Fluorine-free and hydrophobic room-temperature ionic liquids, tetraalkylammonium bis(2-ethylhexyl)sulfosuccinates, and their ionic liquid–water two-phase properties

Fluorine-free and hydrophobic room-temperature ionic liquids (RTILs) composed of the bis(2-ethylhexyl)sulfosuccinate (BEHSS) ion, which is known as the surface-active anion constituting Aerosol OT®, and symmetric tetraalkylammonium ions ((CnH2n+1)4N+; n = 4–8), have been prepared. Physicochemical properties of the water-saturated RTILs such as density, conductivity, viscosity and mutual solubility with water (W) have been measured. The RTIL|W interface is polarizable for the RTILs with n = 5–8 in spite of the high water content, 3.6–8.9 wt% in the water-saturated RTILs. The width of the polarized potential window of the RTIL|W interfaces is quantitatively correlated with the solubility of the RTIL in W. The RTIL–W two-phase systems are not spontaneously emulsified and no reverse micelles are formed in the water-saturated RTILs, although BEHSS− is known to form stable water-in-oil emulsions and reverse micelles in oil–water two-phase systems.

Ultraslow response of interfacial tension to the change in the phase-boundary potential at the interface between water and a room-temperature ionic liquid, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide.

Ultraslow response, on the order of minutes, of the interfacial tension to the change in the phase-boundary potential at the interface between water and a room-temperature ionic liquid, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, has been demonstrated. This ultraslow relaxation, which is not observed at the interface between two immiscible electrolyte solutions made of molecular organic solvents, is likely to be due to the long-range and collective ordering of ions of the electrical double layer on the ionic liquid side of the interface.

Simultaneous observation of nascent plasma and bubble induced by laser ablation in water with various pulse durations

We investigate the effects of pulse duration on the dynamics of the nascent plasma and bubble induced by laser ablation in water. To examine the relationship between the nascent plasma and the bubble without disturbed by shot-to-shot fluctuation, we observe the images of the plasma and the bubble simultaneously by using two intensified charge coupled device detectors. We successfully observe the images of the plasma and bubble during the pulsed-irradiation, when the bubble size is as small as 20 μm. The light-emitting region of the plasma during the laser irradiation seems to exceed the bubble boundary in the case of the short-pulse (30-ns pulse) irradiation, while the size of the plasma is significantly smaller than that of the bubble in the case of the long-pulse (100-ns pulse) irradiation. The results suggest that the extent of the plasma quenching in the initial stage significantly depends on the pulse duration. Also, we investigate how the plasma-bubble relationship in the very early stage affects the shape of the atomic spectral lines observed at the later delay time of 600 ns. The present work gives important information to obtain high quality spectra in the application of underwater laser-induced breakdown spectroscopy, as well as to clarify the mechanism of liquid-phase laser ablation.

On-Site Quantitative Elemental Analysis of Metal Ions in Aqueous Solutions by Underwater Laser-Induced Breakdown Spectroscopy Combined with Electrodeposition under Controlled Potential

We propose a technique of on-site quantitative analysis of Zn(2+) in aqueous solution based on the combination of electrodeposition for preconcentration of Zn onto a Cu electrode and successive underwater laser-induced breakdown spectroscopy (underwater LIBS) of the electrode surface under electrochemically controlled potential. Zinc emission lines are observed with the present technique for a Zn(2+) concentration of 5 ppm. It is roughly estimated that the overall sensitivity over 10 000 times higher is achieved by the preconcentration. Although underwater LIBS suffers from the spectral deformation due to the dense plasma confined in water and also from serious shot-to-shot fluctuations, a linear calibration curve with a coefficient of determination R(2) of 0.974 is obtained in the range of 5-50 ppm.

Temperature dependence of multilayering at the free surface of ionic liquids probed by X-ray reflectivity measurements.

The effect of the temperature on the surface layering of ionic liquids has been studied for two ionic liquids, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide([TOMA(+)][C(4)C(4)N(-)]) and trihexyltetradecylphosphonium bis(nonafluorobutanesulfonyl)amide ([THTDP(+)][C(4)C(4)N(-)]), using X-ray reflectivity measurements at 285, 300, and 315 K. Both [TOMA(+)][C(4)C(4)N(-)] and [THTDP(+)][C(4)C(4)N(-)] develop multilayers at the surface. The structure of the multilayers at the [TOMA(+)][C(4)C(4)N(-)] surface shows little temperature-dependent change, whereas that at the [THTDP(+)][C(4)C(4)N(-)] surface clearly becomes diffused with increasing temperature. The different temperature dependence seems to be related to the difference in the recently reported ultraslow dynamics of the interfacial structure of [TOMA(+)][C(4)C(4)N(-)] and [THTDP(+)][C(4)C(4)N(-)] at the ionic liquid|water interface.

Voltammetric manifestation of the ultraslow dynamics at the interface between water and an ionic liquid.

The ultraslow relaxation (on the order of minutes) of the electrical double-layer structure, related to a change in the phase-boundary potential across the interface between water (W) and the ionic liquid (IL) trioctylmethylammonium bis(nonafluorobutanesufonyl)amide ([TOMA(+)][C(4)C(4)N(-)]) (Y. Yasui et al., J. Phys. Chem. B. 2009, 113, 3273), appears to be invisible in the transfer of tetrapropylammonium ions across the [TOMA(+)][C(4)C(4)N(-)]|W interface, provided that the charging current, which shows an unusual dependence on the voltage scan rate, is subtracted to obtain the faradaic current. This counterintuitive observation can be explained by the differences in the timescales of the fast and slow components of the relaxation dynamics of the electrical double layer on the IL side (ms and min). In contrast, the effect of the slow dynamics becomes surfaced in ion-transfer voltammetry when the ion is surface-active. The transfer of pentadecafluorooctanoate across the [TOMA(+)][C(4)C(4)N(-)]|W interface is irreversible, which is attributable to the self-inhibition of pentadecafluorooctanoate ions transferred to the IL phase. This process is likely to be affected by the ultraslow structural change of the IL side of the interface.

Electrocapillarity under Ultraslow Relaxation of the Ionic Liquid Double Layer at the Interface between Trioctylmethylammonium Bis(nonafluorobutanesulfonyl)amide and Water

Electrocapillarity has been studied in detail at the interface between a hydrophobic ionic liquid (IL), trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, and water, where the ultraslow relaxation of the structure of the electrical double layer on the IL side of the interface exists. The response of the interfacial tension and that of the charging current to the potential step can be fitted by a double exponential model having the relaxation time constants of a few seconds and 100 s. The hysteresis in the interfacial tension in the IL diluted with nitrobenzene persists even in an almost 1:1 mixture of the IL and nitrobenzene. The thermodynamically definable double layer capacitance (C(dl)) estimated from the equilibrated electrocapillary curve, that is, the interfacial tension versus potential curve, at the IL|water interface has a maximum value of about 60 microF cm(-2) in the vicinity of the potential of zero charge (pzc) when the aqueous phase is 0.1 mol dm(-3) LiCl. The C(dl) versus the potential plot shows a characteristic camelback shape, showing a shallow minimum at the pzc, where the C(dl) value is 42 microF cm(-2). This minimum seems to reflect the contribution of C(dl) on the aqueous side of the interface to the total capacitance.