Carbon nanotubes can be functionalized via amidation and esterification of the nanotube-bound carboxylic acids. The solubility of these functionalized carbon nanotubes makes it possible to characterize and study the properties of carbon nanotubes using solution-based techniques. Representative results concerning the solubility, dispersion, defunctionalization, and optical properties of the functionalized carbon nanotubes are presented. Several examples for the use of functionalized carbon nanotubes in the fabrication of polymeric carbon nanocomposites, the probing of nanotube-molecule interactions, and the conjugation with biological species are highlighted and discussed.

Functionalized Carbon Nanotubes: Properties and Applications

Small-diameter (ca. 0.7 nm) single-wall carbon nanotubes are predicted to display enhanced reactivity relative to larger-diameter nanotubes due to increased curvature strain. The derivatization of these small-diameter nanotubes via electrochemical reduction of a variety of aryl diazonium salts is described. The estimated degree of functionalization is as high as one out of every 20 carbons in the nanotubes bearing a functionalized moiety. The functionalizing moieties can be removed by heating in an argon atmosphere. Nanotubes derivatized with a 4-tert-butylbenzene moiety were found to possess significantly improved solubility in organic solvents. Functionalization of the nanotubes with a molecular system that has exhibited switching and memory behavior is shown. This represents the marriage of wire-like nanotubes with molecular electronic devices.

Functionalization of carbon nanotubes by electrochemical reduction of aryl diazonium salts: a bucky paper electrode

There is increased recognition by the world’s scientific, industrial, and political communities that the concentrations of greenhouse gases in the earth’s
atmosphere, particularly CO_2, are increasing. For
example, recent studies of Antarctic ice cores to
depths of over 3600 m, spanning over 420 000 years,
indicate an 80 ppm increase in atmospheric CO_2 in
the past 200 years (with most of this increase
occurring in the past 50 years) compared to the
previous 80 ppm increase that required 10 000 years.2
The 160 nation Framework Convention for Climate
Change (FCCC) in Kyoto focused world attention on
possible links between CO2 and future climate change
and active discussion of these issues continues.3 In
the United States, the PCAST report4 “Federal
Energy Research and Development for the Challenges
of the Twenty First Century” focused attention
on the growing worldwide demand for energy and the
need to move away from current fossil fuel utilization.
According to the U.S. DOE Energy Information
Administration,5 carbon emission from the transportation
(air, ground, sea), industrial (heavy manufacturing,
agriculture, construction, mining, chemicals,
petroleum), buildings (internal heating, cooling, lighting),
and electrical (power generation) sectors of the
World economy amounted to ca. 1823 million metric
tons (MMT) in 1990, with an estimated increase to
2466 MMT in 2008-2012 (Table 1).

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

Spectrofluorimetric data for identified single-walled carbon nanotubes in aqueous SDS suspension have been accurately fit to empirical expressions. These are used to obtain the first model-independent prediction of first and second van Hove optical transitions as a function of structure for a wide range of semiconducting nanotubes. To allow for convenient use in support of spectral studies, the results are presented in equation, graphical, and tabular forms. These empirical findings differ significantly from Kataura plots computed using a simple tight-binding model. It is suggested that the empirically based results should be used in preference to conventional model-based predictions in spectroscopic nanotube research.

Dependence of Optical Transition Energies on Structure for Single-Walled Carbon Nanotubes in Aqueous Suspension: An Empirical Kataura Plot

Substantial separation of single-wall carbon nanotubes (SWNTs) according to type (metallic versus semiconducting) has been achieved for HiPco and laser-ablated SWNTs. We presently argue that stable dispersions of SWNTs with octadecylamine (ODA) in tetrahydrofuran (THF) originate from the physisorption and organization of ODA along the SWNT sidewalls in addition to the originally proposed zwitterion model. Furthermore, the reported affinity of amine groups for semiconducting SWNTs, as opposed to their metallic counterparts, contributes additional stability to the physisorbed ODA. This provides a venue for the selective precipitation of metallic SWNTs upon increasing dispersion concentration, as indicated by Raman investigations.

A Route for Bulk Separation of Semiconducting from Metallic Single-Wall Carbon Nanotubes

Maleic anhydride, a precursor to polyester resins, is made by oxidation of n -butane over vanadium phosphate catalysts. This system is of general interest because it is the only heterogeneously catalyzed, alkane-selective oxidation reaction in commercial use. Time-resolved in situ x-ray absorption spectroscopy shows that when either α I -VOPO 4 /SiO 2 or (VO) 2 P 2 O 7 /SiO 2 catalysts are exposed to n -butane, the rate of maleic anhydride formation is proportional to the rate of decay of V 5+ species in the catalyst. Thus V 5+ species are kinetically significant for the production of maleic anhydride and not just for the production of by-products. The results also suggest that V 5+ species may play a role in the initial hydrogen abstraction from n -butane, the rate-determining step in the reaction sequence. V 4+ sites appear to be responsible for by-product formation.

https://science.sciencemag.org/content/sci/275/5297/191.full.pdf

Gregory K. Bethke

Papers

The Kinetic Significance of V5 in n-Butane Oxidation Catalyzed by Vanadium Phosphates