Short, highly ordered, single-walled mixed-oxide nanotubes assemble from amorphous nanoparticles

J Am Chem Soc. 2007 May 30;129(21):6820-6. doi: 10.1021/ja070124c. Epub 2007 May 5.

Abstract

Nanotubes are important "building block" materials for nanotechnology, but a synthesis process for short (sub-100-nm) solid-state nanotubes with structural order and monodisperse diameter has remained elusive. To achieve this goal, it is critical to possess a definitive mechanistic framework for control over nanotube dimensions and structure. Here we employ solution-phase and solid-state characterization tools to elucidate such a mechanism, particularly that governing the formation of short ( approximately 20 nm), ordered, monodisperse (3.3 nm diameter), aluminum-germanium-hydroxide ("aluminogermanate") nanotubes in aqueous solution. Dynamic light scattering (DLS), vibrational spectroscopy, and electron microscopy show that pH-control of chemical speciation in the aluminogermanate precursor solution is important for producing nanotubes. A combination of DLS, UV-vis spectroscopy, and synthesis variations is then used to study the nanotube growth process as a function of temperature and time, revealing the initial condensation of amorphous nanoparticles of size approximately 6 nm and their transformation into ordered aluminogermanate nanotubes. The main kinetic trends in the experimental data can be well reproduced by a two-step mathematical model. From these investigations, the central phenomena underlying the mechanism are enumerated as: (1) the generation (via pH control) of a precursor solution containing aluminate and germanate precursors chemically bonded to each other, (2) the formation of amorphous nanoscale ( approximately 6 nm) condensates via temperature control, and (3) the self-assembly of short nanotubes from the amorphous nanoscale condensates. This mechanism provides a model for controlled low-temperature (<373 K) assembly of short, monodisperse, structurally ordered nanotube objects.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aluminum Hydroxide / chemistry
  • Germanium / chemistry
  • Light
  • Nanotubes / chemistry*
  • Particle Size
  • Scattering, Radiation
  • Spectrophotometry, Ultraviolet
  • Spectrum Analysis, Raman

Substances

  • Germanium
  • Aluminum Hydroxide