Nanotubs

Published on Web 01/27/2004

Selective Metallic Tube Reactivity in the Solution-Phase
Osmylation of Single-Walled Carbon Nanotubes
Sarbajit Banerjee† and Stanislaus S. Wong*,†,‡
Contribution from the Department of Chemistry; State UniVersity of New York at Stony Brook;
Stony Brook, New York 11794-3400, and Materials and Chemical Sciences Department,
BrookhaVen National Laboratory; Building480; Upton, New York 11973
Received August 25, 2003; E-mail: sswong@notes.cc.sunysb.edu; sswong@bnl.gov

Abstract: Single-walled carbon nanotubes have been reacted with osmium tetroxide (OsO4) in solution in
the presence of O2 and UV irradiation at 254 nm. We observe one main structural motif, namely thickly
coated nanotube structures, densely covered with OsO2, consisting of multiplebundles of derivatized tubes.
In a few instances, bridging uncoated tubes, connecting these thickly coated structures, incorporate a number
of smaller nanotube bundles, projecting out from the larger functionalized aggregates of tubes. It is believed
that OsO2 (a) initially forms on the nanotubes by the preferential covalent sidewall functionalization of metallic
nanotubes and (b) subsequentlyself-aggregates. The formation of an intermediate charge-transfer complex
is likely the basis for the observed selectivity and reactivity of metallic tubes. Extensive characterization of
these osmylated adducts has been performed using a variety of electron microscopy and optical
spectroscopy techniques.

Introduction

In recent years, single-walled carbon nanotubes (SWNTs)
have emerged assignificant building blocks in nanoscale
technology. Their unique structure-dependent mechanical and
electronic properties1 make them of interest in fundamental
science. For instance, the combination of the helicity and
diameter of SWNTs, defined by the roll-up vector, often
determines whether a tube is a metal or a semiconductor.1 They
are thought to have a host of wide-ranging, potentialapplications
including as catalyst supports in heterogeneous catalysis, field
emitters, high strength engineering fibers, sensors, actuators,
tips for scanning probe microscopy, gas storage media, and
molecular wires for the next generation of electronic devices.2-8
The generation of such nanotube-based structures requires
the development of rational nanotube chemistry. Chemical
modification isalso essential to deposition of catalysts and other
species onto nanotube surfaces for nanocatalytic and sensor
applications. Functionalization of carbon nanotubes and the
†
‡

State University of New York at Stony Brook.
Brookhaven National Laboratory.

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10.1021/ja038111w CCC: $27.50 © 2004 American Chemical Society

generation of nanotube-based composites have recently drawn
a lot of attention.9-12 Nanotube sidewalls, end caps, defect sites,
and interiors have been extensively targeted for chemical
derivatization to generate new families of materials with
interesting...