This thesis largely focuses on the mechanistic analysis of the Assembly-Disassembly-
Organisation-Reassembly (ADOR) process through a range of crystallographic techniques
including powder X-ray diffraction and Pair Distribution Function (PDF) analysis and
subsequent analysis using solid-state kinetics.
Chapter 4 describes the development of a new standard protocol to using the ADOR
process. The protocol describes the development of a procedure used for identifying the
optimum conditions (time of reaction, temperature, acidity, etc.) for the ADOR process. In
developing the protocol, Ge-containing UTL zeolites were subjected to hydrolysis
conditions using both water and hydrochloric acid as media, which provides an
understanding of the effects of temperature and pH on the Disassembly (D) and
Organisation (O) steps of the process that define the potential products. Samples were
analysed by powder X-ray diffraction to yield a time course for the reaction at each set of
conditions.
Chapter 5 continues work on the ADOR process and presents the first kinetic study on the
two most prominent steps in the process; Disassembly and Organisation. By using solid-
state kinetic models, Avrami-Erofeev and its linear equivalent Sharp-Hancock, the
dependence on temperature and presence of liquid water was investigated and the activation
energy of the rearrangement process quantified. Work on the rearrangement step aimed to
understand where the silica species intercalates from and which material formed as the
kinetic and thermodynamic product from the reaction.
Chapter 6 describes a study into the Disassembly and Organisation steps of the ADOR
process through in situ Pair Distribution Function (PDF) analysis. This hopes to shed light
on the selectivity of the ADOR process in different media and the mechanism by which the
double-four-ring (d4r) breakdown.
On a different note, Chapter 7 describes the refinement of synthesis conditions used to
prepare poly-crystalline CPO-27-M (MOF-74) with lower concentrations of base and at low
temperature. Refinement of the synthesis of single crystal CPO-27-Mg, -Zn and UTSA-74
was undertaken and the necessary components to forming large single crystals understood
