Takatsugu Wakahara

Fullerene/cobalt porphyrin hybrid nanosheets with ambipolar charge transporting characteristics.

A novel supramolecular nanoarchitecture, comprising C(60)/Co porphyrin nanosheets, was prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of optical microscopy, AFM, STEM, TEM, and XRD. It is established that the highly crystalline C(60)/Co porphyrin nanosheets have a simple (1:1) stoichiometry, and when incorporated in bottom-gate, bottom-contact field-effect transistors (FETs), they show ambipolar charge transport characteristics.

Preparation and Optical Properties of Fullerene/Ferrocene Hybrid Hexagonal Nanosheets and Large-Scale Production of Fullerene Hexagonal Nanosheets

The supramolecular nanoarchitectures, C(60)/ferrocene nanosheets, were prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of SEM, STEM, HRTEM, XRD, Raman and UV-vis-NIR spectra. The highly crystallized C(60)/ferrocene hexagonal nanosheets had a size of ca. 9 microm and the formulation C(60)(ferrocene)(2). A strong charge-transfer (CT) band between ferrocene and C(60) was observed at 782 nm, indicating the presence of donor-acceptor interaction in the nanosheets. Upon heating the nanosheets to 150 degrees C, the CT band disappeared due to the sublimation of ferrocene from the C(60)/ferrocene hybrid, and C(60) nanosheets with an fcc crystal structure and the same shape and size as the C(60)/ferrocene nanosheets were obtained.

Photoinduced charge separation in three-layer supramolecular nanohybrids: fullerene–porphyrin–SWCNT

Photoinduced charge separation processes of three-layer supramolecular hybrids, fullerene-porphyrin-SWCNT, which are constructed from semiconducting (7,6)- and (6,5)-enriched SWCNTs and self-assembled via π-π interacting long alkyl chain substituted porphyrins (tetrakis(4-dodecyloxyphenyl)porphyrins; abbreviated as MP(alkyl)(4)) (M = Zn and H(2)), to which imidazole functionalized fullerene[60] (C(60)Im) is coordinated, have been investigated in organic solvents. The intermolecular alkyl-π and π-π interactions between the MP(alkyl)(4) and SWCNTs, in addition, coordination between C(60)Im and Zn ion in the porphyrin cavity are visualized using DFT calculations at the B3LYP/3-21G(*) level, predicting donor-acceptor interactions between them in the ground and excited states. The donor-acceptor nanohybrids thus formed are characterized by TEM imaging, steady-state absorption and fluorescence spectra. The time-resolved fluorescence studies of MP(alkyl)(4) in two-layered nanohybrids (MP(alkyl)(4)/SWCNT) revealed efficient quenching of the singlet excited states of MP(alkyl)(4) ((1)MP*(alkyl)(4)) with the rate constants of charge separation (k(CS)) in the range of (1-9) × 10(9) s(-1). A nanosecond transient absorption technique confirmed the electron transfer products, MP˙(+)(alkyl)(4)/SWCNT˙(-) and/or MP˙(-)(alkyl)(4)/SWCNT˙(+) for the two-layer nanohybrids. Upon further coordination of C(60)Im to ZnP, acceleration of charge separation via(1)ZnP* in C(60)Im→ZnP(alkyl)(4)/SWCNT is observed to form C(60)˙(-)Im→ZnP˙(+)(alkyl)(4)/SWCNT and C(60)˙(-)Im→ZnP(alkyl)(4)/SWCNT˙(+) charge separated states as supported by the transient absorption spectra. These characteristic absorptions decay with rate constants due to charge recombination (k(CR)) in the range of (6-10) × 10(6) s(-1), corresponding to the lifetimes of the radical ion-pairs of 100-170 ns. The electron transfer in the nanohybrids has further been utilized for light-to-electricity conversion by the construction of proof-of-concept photoelectrochemical solar cells.

Preparation of Composite Films of a Conjugated Polymer and C60NWs and Their Photovoltaic Application

Composite films of conjugated polymers, such as poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT), with C60 nanowhiskers (C60NWs) were prepared. The photoluminescence originating from the conjugated MDMO-PPV polymers was effectively quenched in the composite film, indicating a strong interaction between the conjugated polymer and C60NWs. The photovoltaic devices were fabricated using C60NW (conjugated polymer) composite films, resulting in a power conversion efficiency of ~0.01% for P3HT with short length thin C60NWs, which is higher than that previously reported for thick C60 nanorods. The present study gives new guidance on the selection of the type of C60NWs and the appropriate polymer for new photovoltaic devices.

Electrochemical Characterization of Catalytic Activities of C60 Nanowhiskers to Oxygen Reduction in Aqueous Solution

We have investigated the catalytic function and activity of C60 nanowhiskers (C60NWs) on glassy carbon electrodes to the electrochemical O2 reduction in aqueous solution by cyclic voltammetry. It is found that C60NWs are active catalysts for O2 reduction in aqueous solution, although pristine C60 powders do not show any activities. The porous and conductive features of C60NWs play important roles in the electrochemical O2 reduction.

The Influence of Water and Temperature on the Solubility of C60 in Pyridine Solution

The dependence of Fullerene’s solubility on both molecular structure of the solvent and temperature must be understood in order to optimize the growth condition of C60 nanotubes (C60NTs) prepared by a modified liquid–liquid interfacial precipitation method. We explore the influence of small amounts of water dissolved in pyridine on the solubility of C60. We observe a decreasing solubility of Fullerene as a function of increasing water content. This result is confirmed by a kinetics study of the Fullerene C60 and pyridine reaction in the presence of water. The activation energy of C60 in pyridine solution become important with increasing water content. We have also investigated the effect of incubation temperature on the solubility of C60 in pyridine solution. The solubility of Fullerene is maximum when the incubation temperature is 273xa0K.