Thermogravimetric analysis (TGA) has demonstrated that multiwalled nanotubes (MWNTs) annealed at 2200 to 2800 °C are more air stable than as-produced MWNTs, diamond, graphite, and annealed diamond. The annealed MWNTs are similar in stability to annealed graphite. Defect sites along the walls and at the ends of the raw MWNTs facilitate the thermal oxidative destruction of the nanotubes. Thermal annealing removes these defects, thereby providing MWNTs with enhanced air stability.
Treatment of fullerenes with reducing metals and a
proton source leads to the formation of
hydrogenated fullerenes (C60H
n
and
C70H
n
). The reaction of
C60 with a variety of metals was
investigated, using metals that span a broad range of reducing power,
from tin (E° = −0.14 V) to
magnesium (E° = −2.36 V). We report useful
synthetic routes to a number of reduced fullerenes,
including C60H2, C60H4,
and C60H6, and we have determined that, despite
the huge number of isomers
that are possible, a small number are actually formed in these cases.
For example, only two isomers
of C60H6 are obtained in the Zn(Cu) reduction
of C60, in a 6:1 ratio. Three isomers of
C70H10 are
produced, in ratios that are dependent on reaction time.
13C NMR chemical shift assignments for 1,2-C60H2 (1) and a series of 13C-labeled fullerene derivatives with three-, four-, and five-membered annulated rings (2-4) were assigned using 2D INADEQUATE spectroscopy and examined for trends that correspond to the changes in strain in the fullerene cage. Chemical shifts of equivalent carbons from 1-4 show that eight carbons trend downfield (carbons 5, 7, 8, 9, 11, 15, 16, 17) and the remaining six carbons (4, 6, 10, 12, 13, 14) trend upfield with increasing ring size. While the average chemical shift is nearly constant, the dispersion is greatest when the local strain is the least, in 1,2-C60H2 (1). 13C chemical shifts are not well correlated with trends in ring size, with strain as measured by the pyramidalization angle of nearby carbons, or with the geometry of the fullerene cage. We interpret the results as evidence that subtle geometrical changes lead to modulation of the strength of ring currents near the site of addition and, in turn, the magnetic field generated by these ring currents affects the chemical shift of carbons on the far side of the fullerene core. These results highlight ring currents as being critically important to the determination of 13C chemical shifts in fullerene derivatives.
We report an improved chromatographic purification of soluble single-walled carbon nanotubes (s-SWNTs) using gel permeation chromatography. Three fractions are separated by gel permeation chromatography, and the first fraction contains 74% of the s-SWNTs as detected by atomic force microscopy and UV and near-infrared spectroscopy.
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