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Endo- and exohedral carbon nanotube hybrids: Preparation and spectroscopic characterisation

Posted on:2009-07-09Degree:DrType:Thesis
University:Universiteit Antwerpen (Belgium)Candidate:Cambre, SofieFull Text:PDF
GTID:2441390005450089Subject:Chemistry
Abstract/Summary:
One of the most fascinating properties of carbon nanotubes (CNTs) is that their external surface as well as their inner hollow space can be used to adsorb or encapsulate various molecules, thereby creating so-called exo- and endohedral nanohybrids that combine the properties of the individual components with new functionalities which originate from the interaction between both materials. In this thesis, different endo- and exohedral CNT-hybrids are investigated by means of a range of spectroscopic techniques, in particular UV/Vis absorption, steady-state and time-resolved fluorescence, resonant Raman scattering (RRS) and electron paramagnetic resonance (EPR).;The solubilisation of the CNTs with bile salt surfactants, yielding highly concentrated solutions of individually isolated CNTs in water, is investigated with spin-probe EPR. The spin-probe is incorporated inside the micellar layer wrapping the CNTs and the dynamics and orientation of this spin-probe is studied by EPR.;In this thesis it is demonstrated that the encapsulation of water in pre-opened CNTs can be probed by resonant Raman scattering of the radial breathing modes of the CNTs. The frequencies of these modes, as well as the electronic resonances of the CNTs are shifted upon water-filling. Therefore it was possible to set up a technique to quantitatively monitor the opening/closing and water-filling of CNTs after different chemical and mechanical treatments.;Exohedral porphyrin/CNT hybrids were prepared and investigated by EPR. It was found that metallic CNTs are stronger pi-acceptors than semiconducting CNTs. After solubilising the nanohybrids using bile salts, we obtained, for the first time, the isolated nanohybrids in solution in the pure form. The absorption spectrum of these porphyrins in the nanohybrids is strongly red shifted compared to the free porphyrin absorption. In addition also a quasi-complete quenching of the porphyrin fluorescence is observed.;Finally endohedral CNT hybrids, using paramagnetic molecules, were prepared and investigated. The EPR spectrum of the encapsulated molecules can be clearly distinguished from the non-encapsulated molecules. Analyzing the EPR line widths, it was found that the encapsulated molecules are closely spaced. Furthermore, from orientation dependent measurements of aligned CNT films we could obtain information on the orientational distribution of the molecules inside the CNTs.
Keywords/Search Tags:Cnts, Molecules, EPR, Exohedral, Hybrids
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