A 2006 editorial written by Marc Monthioux and Vladimir Kuznetsov in the journal Carbon described the interesting and often-misstated origin of the carbon nanotube. A large percentage of academic and popular literature attributes the discovery of hollow, nanometer-size tubes composed of graphitic carbon toSumio Iijima of NEC in 1991.
In 1952 L. V. Radushkevich and V. M. Lukyanovich published clear images of 50 nanometer diameter tubes made of carbon in the Soviet Journal of Physical Chemistry. This discovery was largely unnoticed, as the article was published in the Russian language, and Western scientists’ access to Soviet press was limited during the Cold War. It is likely that carbon nanotubes were produced before this date, but the invention of the transmission electron microscope (TEM) allowed direct visualization of these structures.
Carbon nanotubes have been produced and observed under a variety of conditions prior to 1991. A paper by Oberlin, Endo, and Koyama published in 1976 clearly showed hollow carbon fibers with nanometer-scale diameters using a vapor-growth technique. Additionally, the authors show a TEM image of a nanotube consisting of a single wall of graphene. Later, Endo has referred to this image as a single-walled nanotube.
In 1979, John Abrahamson presented evidence of carbon nanotubes at the 14th Biennial Conference of Carbon at Pennsylvania State University. The conference paper described carbon nanotubes as carbon fibers that were produced on carbon anodes during arc discharge. A characterization of these fibers was given as well as hypotheses for their growth in a nitrogen atmosphere at low pressures.
In 1981, a group of Soviet scientists published the results of chemical and structural characterization of carbon nanoparticles produced by a thermocatalytical disproportionation of carbon monoxide. Using TEM images and XRD patterns, the authors suggested that their “carbon multi-layer tubular crystals” were formed by rolling graphene layers into cylinders. They speculated that by rolling graphene layers into a cylinder, many different arrangements of graphene hexagonal nets are possible. They suggested two possibilities of such arrangements: circular arrangement (armchair nanotube) and a spiral, helical arrangement (chiral tube).
In 1987, Howard G. Tennett of Hyperion Catalysis was issued a U.S. patent for the production of “cylindrical discrete carbon fibrils” with a “constant diameter between about 3.5 and about 70 nanometers…, length 102 times the diameter, and an outer region of multiple essentially continuous layers of ordered carbon atoms and a distinct inner core….”
Iijima’s discovery of multi-walled carbon nanotubes in the insoluble material of arc-burned graphite rods in 1991 and Mintmire, Dunlap, and White’s independent prediction that if single-walled carbon nanotubes could be made, then they would exhibit remarkable conducting properties helped create the initial buzz that is now associated with carbon nanotubes. Nanotube research accelerated greatly following the independent discoveries by Bethune at IBM and Iijima at NEC of single-walled carbon nanotubes and methods to specifically produce them by adding transition-metal catalysts to the carbon in an arc discharge. The arc discharge technique was well-known to produce the famed Buckminster fullerene on a preparative scale, and these results appeared to extend the run of accidental discoveries relating to fullerenes. The original observation of fullerenes in mass spectrometry was not anticipated, and the first mass-production technique by Krätschmer and Huffman was used for several years before realizing that it produced fullerenes.
The discovery of nanotubes remains a contentious issue. Many believe that Iijima’s report in 1991 is of particular importance because it brought carbon nanotubes into the awareness of the scientific community as a whole.