Single-walled carbon nanotubes as a reducing agent for the synthesis of a Prussian blue-based composite: a quartz crystal microbalance study.

We investigated the synthesis mechanism of Prussian blue (PB) crystals supported on single-walled carbon nanotubes (SWCNTs), by performing in situ quartz crystal microbalance (QCM) measurements to probe the change in the electrode mass during the reaction, and using photoirradiation at designated stages of the process. We found that in contrast to existing hypotheses, light irradiation played no role in the synthesis process of Prussian blue on SWCNTs. On the other hand, the number of electrons transferred per one mole of the obtained product, and the number of electrons transferrable from SWCNTs, calculated from the density of states (DOS) of the SWCNTs in the sample, both favor the hypothesis of the reaction being triggered by direct electron transfer from SWCNTs to Fe3+, which occurs because of the energy difference between the Fermi level of SWCNTs and redox potential of Fe3+ ions.

One-step synthesis of visible light CO2 reduction photocatalyst from carbon nanotubes encapsulating iodine molecules.

We describe the synthesis and visible-light CO2 photoreduction catalytic properties of a three-component composite consisting of AgI, AgIO3, and single-walled carbon nanotubes (SWCNTs). The catalyst is synthesized by immersing SWCNTs encapsulating iodine molecules in AgNO3 aqueous solution, during which neutral iodine (I2) molecules encapsulated in SWCNTs transform disproportionately to I5+ (AgIO3) and I- (AgI), as revealed from the characterization of the composite by Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In addition, photoirradiation experiments using a solar-simulator (AM1.5G) showed that the obtained three-component composite works as a CO2 photoreduction catalyst under visible light despite the wide band gap of AgIO3, suggesting possible transfer of the visible light-excited electron from AgI via SWCNTs.

Switching of alternative electrochemical charging mechanism inside single-walled carbon nanotubes: a quartz crystal microbalance study.

We probed electrochemical ion storage in single-walled carbon nanotubes (SWCNTs) of different diameters in two different organic electrolytes using electrochemical quartz crystal microbalance (EQCM) tracking. The measurements showed that charge storage probed by cyclic voltammetry did not deteriorate when steric effects seemed to hinder the accessibility of counter-ions into SWCNTs, and instead proceeded predominantly by co-ion desorption, as was shown by the decrease in the electrode mass probed by EQCM. The dominant mechanism correlated with the SWCNT diameter/ion size ratio; counter-ion adsorption dominated in the whole potential range when the diameter of SWCNTs was comparable to the size of the largest ion, whereas for larger diameters the charge increase coincided with a decrease in the electrode mass, indicating the dominance of co-ion desorption. The dominance of co-ion desorption was not observed in activated carbon, nor was it previously reported for other carbon materials, and is likely switched on because the carrier density of SWCNT increases with applied potential, and maintains the electrode capacity by co-ion desorption to overcome the steric hindrances to counter-ion adsorption.

The effect of diameter size of single-walled carbon nanotubes on their high-temperature energy storage behaviour in ionic liquid-based electric double-layer capacitors.

We investigated the effect of the diameter size of single-walled carbon nanotubes (SWCNTs), on their high-temperature energy storage behavior in an electric double layer capacitor (EDLC) using the ionic liquid triethyl(2-methoxyethyl) phosphonium bis(trifluoromethylsulfonyl)imide (P222(2O1)-TFSI). We used four SWCNT samples with diameter sizes ranging from 0.8 to 5 nm, and evaluated their electrochemical charge storage behavior through galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). We found that for the SWCNTs with small average diameter of 1 nm, the value of the electrode capacitance measured at a current density of 5 mA g-1 increased from 15.8 at room temperature to 27.5 F g-1 at 150 °C, and the value measured at a current density of 80 mA g-1 increased from 14.0 at room temperature to 22.1 F g-1 at 150 °C. The larger diameter samples on the other hand did not show any significant change in their capacitance with temperature. We calculated the size of the interstitial tube spaces from the Raman spectra of the samples, and used density functional theory (DFT) calculations to estimate the sizes of the cation and anion of the electrolyte. The obtained results suggest that the temperature-induced changes in the electrolyte properties improved the ion accessibility into the otherwise constrained space inside the small diameter SWCNTs, while the spaces inside the larger SWCNTs already provided easily accessible storage sites hence good performance at room temperature, making the increase in temperature of little to no effect on the charge storage performance in such SWCNTs.

High ion adsorption densities of site-selective nitrogen doped carbon sheets prepared from natural lignin.

Carbon fibers and sheets were prepared from jet-milled natural chitin and cellulose samples, and from natural lignin sample using ice-templating technique, respectively. Nitrogen doping treatments using melamine were also performed for the carbon fibers and sheets. Electric double layer capacitor (EDLC) electrode properties of the prepared carbon fibers and sheets including the nitrogen doped samples were investigated with aqueous (sulfuric acid) and organic (tetraethylammonium tetrafluoroborate in propylene carbonate) electrolytes. It was found that the nitrogen doped lignin carbon sheets having very small specific surface area of 66 m2 g-1 show very high EDLC capacitances of 227 F g-1 and 80 F g-1 determined by charge-discharge measurements at current density of 50 mA g-1 for aqueous and organic electrolytes, respectively. X-ray photoelectron spectroscopy (XPS) measurements revealed that nitrogen atoms of the nitrogen doped lignin carbon sheets exist dominantly in pyridinic sites unlike other chitin and cellulose carbon fibers. We discussed that this site-selective nitrogen doping gives exceptionally high ion adsorption density per unit surface area of the nitrogen doped lignin carbon sheets.

Alkali Metal Ion Storage of Quinone Molecules Grafted on Single-Walled Carbon Nanotubes at Low Temperature.

9,10-Anthraquinone and 9,10-phenanthrenequinone (PhQ) were grafted onto two kinds of single-walled carbon nanotube (SWCNT) samples having different mean tube diameters by diazo-coupling reactions. The structural details of PhQ-grafted SWCNT (PhQ/SWCNT) samples were analyzed by X-ray diffraction and Raman measurements. It was discussed that a few-nanometer-thick layer of polymerized PhQs covers the outside of SWCNT bundles. The obtained PhQ/SWCNT works very well as lithium-ion battery and sodium-ion battery electrodes, not only at room temperature but also at 0 °C. It should be noted that the cycle performance of the PhQ/SWCNT electrode is much better than that of PhQ encapsulated in SWCNT (PhQ@SWCNT). We also calculated molecular base reaction energies by density functional theory calculations to gain a qualitative insight into the observed discharge potentials of the PhQ/SWCNT electrode.

Electrochemical lithium-ion storage properties of quinone molecules encapsulated in single-walled carbon nanotubes.

We investigated the electrochemical lithium-ion storage properties of 9,10-anthraquinone (AQ) and 9,10-phenanthrenequinone (PhQ) molecules encapsulated in the inner hollow core of single-walled carbon nanotubes (SWCNTs). The structural properties of the obtained encapsulated systems were characterized by electron microscopy, synchrotron powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. We found that almost all quinone molecules encapsulated in the SWCNTs can store Li-ions reversibly. Interestingly, the undesired capacity fading, which comes from the dissolution of quinone molecules into the electrolyte, was suppressed by the encapsulation. It was also found that the overpotential of AQ was decreased by the encapsulation, probably due to the high-electric conductivity of SWCNTs.

Spectroscopic evidence for the origin of the dumbbell cyclic voltammogram of single-walled carbon nanotubes.

We investigated the changes in charge carrier density responsible for the dumbbell-like cyclic voltammogram of single-walled carbon nanotubes (SWCNTs) used as electric double layer capacitor electrodes. We utilized in situ Raman spectroscopy of SWCNTs in the potential range where the dumbbell voltammogram is observed and electric double layer charging would be the dominant mechanism. The study revealed that, unexpectedly, the spectroscopic changes coinciding with the dumbbell steps on the voltammogram occur more sharply in metallic tubes, as seen from (1) the sudden enhancement in the intensity of the BWF Breit-Wigner-Fano (BWF) feature, (2) a considerably more significant frequency upshift of G(+) and G' bands, and (3) a drop in radial breathing mode intensity, compared to those in the spectra of semiconducting tubes. In addition, the spectroscopic changes observed with open-end SWCNT samples were more defined and correlated more accurately with the electronic structure of the tubes compared to those observed with closed-end SWCNTs.

Temperature-dependent water solubility of iodine-doped single-walled carbon nanotubes prepared using an electrochemical method.

We demonstrate that iodine-doping into single-walled carbon nanotubes (SWCNTs) can be effectively done using an electrochemical method. It is shown by in situ Raman measurements that the iodine-doping level can be easily and finely controlled because de-doping is also possible by changing the polarity. In situ synchrotron XRD measurements reveal that iodine molecules are mainly inserted into the hollow core of SWCNTs. The dispersion state of the iodine-doped SWCNTs in water as a function of temperature is also investigated. It is shown that the iodine-doped SWCNTs can be homogeneously dispersed in water at low temperature (ca. <15 °C).

Ion adsorption on the inner surface of single-walled carbon nanotubes used as electrodes for electric double-layer capacitors.

In the present study, ion adsorption on the outer and inner surfaces of single-walled carbon nanotubes (SWCNTs) in different aqueous and organic electrolytes was analysed. It was found that the fundamental properties of tube size and electronic structure, particularly the transition between van Hove singularities (the band gap), reflected by the shape of the cyclic voltammogram and increase in the number of charge carriers upon doping, apparently provided additional energy for ion adsorption inside open-end SWCNTs. In addition, when cyclic voltammograms recorded at different potential scan rates were observed, the outer surface of the tubes demonstrated the behaviour of a flat electrode with less dependence on the potential scan rate when compared to the inner surface, which acts as a porous electrode showing an ohmic drop and a distorted voltammogram at high scan rates. Mathematical analysis showed that opening the inner channel of the tubes increases electrode resistance, and that the magnitude of variation in the resistance depends on the type of electrolyte.