Thermal decomposition of carbon precursors in decorated AFI zeolite crystals.

Mass spectrometry and thermogravimetric analysis are used to explore the thermal decomposition of carbon precursors (primarily the tripropylammonium cations) occluded within AlPO(4)-5 (AFI) crystals prepared in various media (in the presence or absence of F(-) ions, Si(4+) substations of P(5+)), with the aim to fabricate high-density 0.4-nm single-walled carbon nanotubes (SWNTs). It has been found that the tripropylammonium precursors exist in the as-synthesized crystals in three different forms: tripropylammonium fluoride, hydroxide, and tripropylammonium cation compensating for the negative charge of the framework. The latter is bonded to the framework by strong chemical interaction and its decomposition takes place by a series of beta-elimination reactions to give propylene and ammonia, with the stepwise formation of dipropylammonium and n-propylammonium cations. The 0.4-nm SWNTs filling density was found to be higher than that resulting from the carbon precursor of tripropylammonium fluoride and hydroxide, because of the strong adsorption force of the channel walls to pyrolysate, as evidenced by the clear and strong radial breathing modes in Raman spectra.

Geometry, phase stability, and electronic properties of isolated selenium chains incorporated in a nanoporous matrix.

We report the fabrication process of isolated one-dimensional Se chains incorporated in the matrix of AlPO4-5 single crystals and the experimental investigation of the geometry, phase stability, electronic properties, and electron-phonon coupling effect of these Se chains. The structure of the helical Se chains inside the channels is discussed on the basis of X-ray scattering measurements. Thermal analysis and temperature-dependent micro-Raman measurements show that Se single chains are flexible and can convert from a weak distorted phase into another phase with strongly disordered structure ("melting" state) around 340 K. Since the electrons are confined in the one-dimensional channels, the absorption band of the Se chain is obviously blue shifted compared with that of trigonal Se. With increasing temperature, this band shifts linearly to the lower energy side, in sharp contrast to the nonlinear temperature coefficient of trigonal Se, which is attributed to the greatly diminished interchain interaction and the weakening of the electron-optical phonon coupling in a low-dimensional system. In the vicinity of the absorption band, both first-order and second-order Raman signals for the Se chain are enhanced, due to the strong electron-phonon coupling when the excitation laser energy matches the electronic transition in isolated Se chains.