MRS Proceedings

Table of Contents - Volume  453  - Symposium R – Solid State Chemistry of Inorganic Materials  

Editors : Peter K. Davies, Allan J. Jacobson, Charles C. Torardi, Terrell A. Vanderah


Examples of Hydrothermal Titration and Real Time X-Ray Diffraction in the Synthesis of Open Frameworks

1996 MRS Fall Meeting.

J. B. Parisea1a2, K. Tana1, P. Norbya3, Y. Koa1 and C. Cahilla2

a1 Earth and Space Sciences, State University of New York, StonyBrook, NY 11794–2100

a2 Department of Chemistry, State University of New York, StonyBrook, NY 11794–2100

a3 Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11973


Hydrothermal titration (HTT) techniques represent a new synthetic strategy for the production of open frameworks. As an example, initial digestion of amorphous GeS2 in the presence of tetraethyl ammonium hydroxide (TEAOH) at 100°C is followed by injection of Ag+ into this mixture to condense the [Ge4S10]4− clusters and form a framework consisting of 8-ring channels bounded by alternating GeS-clusters and Ag+. The rational use of this apparatus depends upon determining the timing of injection. Insight into the changes occurring during reactant digestion is provided by real time synchrotron X-ray powder diffraction. Changes in the the system dimethylamine-Sb-S have been followed in real time at different temperatures. The transformation from mixtures of DMA, Sb and S to the known open phase DMA-SbS-SB8 was followed by observing monochromatic X-ray scattering detected on an imaging plates over a 8 hr period with one continuous exposure.