Shuhei Inoue

Upconversion mechanism in Er3+-doped fluorozirconate glasses under 800 nm excitation

The upconversion emission intensities of Er3+ ion around 550 and 660 nm in fluorozirconate glasses were measured under 800 nm excitation. Though energy transfer processes played an important role in upconversion mechanism at high concentration of ErF3, those have not been treated quantitatively. The energy transfer rates were calculated from the optical parameters assuming some distribution of Er3+ ions. We calculated the upconversion intensities around 550 and 660 nm by using rate equations. It was found that the dependence of upconversion emission intensities on the ErF3 concentration could be reproducible and the principal upconversion mechanism could be evaluated.

Effect of Yb3+ doping on upconversion emission intensity and mechanism in Er3+/Yb3+-codoped fluorozirconate glasses under 800 nm excitation

Er3+ singly- and Er3+/Yb3+-codoped fluorozirconate glasses were prepared. The upconversion emission intensities of the Er3+ ion around both 550 and 660 nm were measured under 800 nm excitation. The absorption band of the Yb3+ ion is located around 980 nm. Though the absorption band of Yb3+ does not interact directly with the incident light at 800 nm, both upconversion intensities around 550 and 660 nm emission increased with the increasing YbF3 concentration. We calculated the upconversion intensities around 550 and 660 nm by using rate equations and evaluated the principal upconversion mechanism in Er3+ singly- and Er3+/Yb3+-codoped samples quantitatively. We also investigated the reason for the increase of the upconversion emission intensities with the codoping of Yb3+ under 800 nm excitation.

Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition Synthesis of Carbon Nanotubes

The chemical reactions of transition metal clusters in the gas phase have aroused considerable scientific interest and are also of critical scientific importance. For example, these reactions are involved in the synthesis of single-walled carbon nanotubes, which are considered ideal materials because of their outstanding properties. Alcohol catalytic chemical vapor deposition (ACCVD) is one of the best synthetic processes for carbon nanotubes (CNTs); however, even the initial growth mechanism is still unclear, unlike those of other synthetic processes. In this study, we used a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer to determine the initial reactions of transition metal cluster ions (iron, cobalt, and nickel) that are typically adopted in the alcohol CVD process. Metal clusters with approximately 10–25 atoms each, generated by a pulsed laser ablation system in a supersonic-expansion cluster beam source, were directly carried into the FT-ICR cell. Subsequently, ethanol was introduced into the ICR cell. We observed two different results: one was simple chemisorption observed in the iron cluster and the other was dehydrogenated chemisorption observed in the nickel cluster; however, cobalt clusters exhibited both patterns, and a sequential reaction was observed. Furthermore, the dehydrogenation of ethanol on the cobalt cluster is fully described from isotope-labeled experiments.

Estimation of adsorption energy for water molecules on a multi-walled carbon nanotube thin film by measuring electric resistance

Gas sensors based on carbon nanotube (CNT) films have attracted attention owing to their low power consumption. For further development of these sensors, we need to understand the surface interaction of the films with gas molecules. In our previous research, we investigated the influence of water molecules on the electrical conductance of multi-walled CNT films and explained this phenomenon using a two-layer adsorption model. This work motivated us to measure the adsorption energy of CNT-H2O. In this study, we focused on the first-layer adsorption and investigated the sheet resistance to water vapor pressure at various temperatures using the transmission line method (TLM). The results were fitted to Langmuir adsorption model and the adsorption equilibrium constant was determined. The temperature dependence of the sheet resistance followed a model of fluctuation induced tunneling (FIT), in which the energy barrier at the CNT junction is regarded as the main factor influencing the electrical conductance of ...

FT-ICR studies of laser vaporized clusters from Ni/Co- and Ni/Y-loaded graphite samples

Abstract Metal-carbon binary clusters generated by the laser vaporization of Ni/Co- and Ni/Y-loaded graphite samples used for the macroscopic production of SWNTs were studied. Positive and negative clusters generated by the laser-vaporization supersonic-expansion cluster beam source were directly injected into the FT–ICR mass spectrometer. The chemical reaction of these clusters with NO was used as the probe of the geometrical structure of clusters. It was speculated that a few Ni or Co atoms attached outside of imperfect carbon cage for Ni/Co loaded case, and that Y atom was included in the carbon cage for Ni/Y loaded case.

In situ mass spectrometry of glucose decomposition under hydrothermal reactions

We designed an in situ mass spectrometry (in situ MS) analysis method and developed to identify the products of glucose decomposition under hydrothermal condition for the first time. The in situ MS analysis was performed by coupling a tubular batch reactor with a quadrupole mass analyzer via custom-built connection fittings. The products of glucose decomposition were investigated by in situ MS, mass spectrometry of cold effluent, and high-performance liquid chromatography (HPLC) analysis of cold effluent and the results were compared. At 140 °C, in situ MS and mass spectrometry of cold effluent showed that the decomposition of glucose does not proceed; this was confirmed by comparison with the mass spectral database for glucose. At 180 °C or higher, a clear base fragmentation peak of 5-hydroxymethylfurfural (5-HMF) at position m/z 97 and that of furfural at m/z 96, formic acid (m/z=46) and levulinic acid (m/z=116) were observed by mass spectrometry. No levulinic acid or furfural was observed through conventional HPLC analysis under any condition; only glucose, formic acid, and 5-HMF could be detected. The effectiveness of in situ MS analysis is clear, compared to mass spectrometry analysis of cold effluent and HPLC analysis.

Transport phenomena of electrons at the carbon nanotube interface with molecular adsorption

The electric conductance of carbon-nanotube (CNT) films is affected by gas adsorption. Previous studies have shown that the adsorption of gas molecules on the CNT/CNT interface is the key to the changing CNT-film conductance. However, it is still unclear how the gas molecules affect the electric conduction of the CNT/CNT interface or its electron transport properties. We present here a study on the effects of gas-molecule adsorption on the CNT/CNT interface using a fluctuation-induced tunneling (FIT) model of the CNT-film electrical conduction. We demonstrated that the CNT-film conduction follows the FIT model, and the subsequently estimated electrostatic potential between the CNT/CNT interfaces was in good agreement with estimates from density functional theory simulations. Since the FIT model treats the CNT/CNT interface as a parallel-plate capacitor, we propose a modified FIT model that accounts for the change in the dielectric constant at the CNT/CNT interface due to the adsorption of gas molecules. T...

Inhibition of char deposition using a particle bed in heating section of supercritical water gasification

Supercritical water gasification (SCWG) has attracted attention as a technology for utilizing wet biomass. We used a fluidized bed of alumina particles to prevent blockage of a SCWG reactor. A glucose solution was heated in the reactor with and without fluidized alumina particles. In the absence of alumina particles, char particles formed homogeneously in the reactor, but the use of a fluidized bed resulted in accumulation of char particles at the reactor’s exit rather than inside the reactor. Therefore, the fluidized bed was effective at preventing blockage of the reactor. However, the alumina particles did not remove deposits from the reactor’s walls. Instead, the fluidized bed caused larger char particles to form, preventing their adhesion to the reactor’s wall.

Molecular Dynamics Approach for the Effect of Metal Coating on Single-Walled Carbon Nanotube

The functionalized single-walled carbon nanotube (SWCNT) is focused lately, but there is no guarantee to keep its outstanding properties. In this paper the physical strength of a SWCNT is derived in terms of a stress-strain curve by molecular dynamics simulation. The breaking stress of a metal-coated SWCNT was lower than that of an uncoated SWCNT; however, the force constant increased by 17%, which can be attributed to the effect of the metal coating on the SWNCT. With regard to the rupture phenomena, it was observed that the uncoated SWCNT ruptured more easily than the metal-coated SWCNT at the rupture point. The rupture phenomenon was initiated by a local distortion of the metal atoms of the SWCNT.

Influence of catalyst supporters on catalyst nanoparticles in synthesis of single-walled carbon nanotubes

It is important to understand catalytic reactions involved in synthesizing carbon nanotubes. Usually, catalysts are used with supporters for better stability and influences of supporters on catalysis is negligible; however, catalysts used for synthesizing single-walled carbon nanotubes are too small to neglect their influence. Here, we experimentally investigated efficiencies of commonly used catalyst supporters such as magnesium oxide, zeolite, and aluminum oxide when they were combined with iron-cobalt, which is a typical catalyst. It was observed that zeolite-supported catalysts could synthesize single-walled carbon nanotubes, while the others could not. Cluster molecular orbital calculations showed that electronic states of catalysts supported by MgO in the boundary layer between catalysts and supporters were restricted due to covalent bonding between cobalt and magnesium. Density functional theory calculations indicated that catalysts on zeolite had enough electrical orbital near Fermi level and they widely spread over catalysts surface, but catalysts on MgO did not. This characteristic can affect catalytic activities.