Synthesis, structures and properties of inorganic framework materials

Abstract

Chapter 1 reviews the literature on the structures and properties of inorganic framework materials that are of relevance to this thesis. In particular the phenomenon of negative thermal expansion and the AM(_2)O(_8)/AM(_2)O(_7) families of materials are discussed. Chapter 2 describes the methods of synthesis and characterisation of the materials investigated in this thesis. Chapter 3 discusses the dehydration reaction of M(_o)O(_2).H(_2)O.PO(_3)OH. The study involved the introduction of a new methodology for whole pattern powder fitting; this method was later verified by full Rietveld analysis. This investigation led to the discovery and structure solution of two new molybdenum phosphates using powder XRD. These materials have been named β-(MoO(_2))(_2)P(_2)0(_7) and β -(Mo0(_2))(_2)P(_2)0(_7). A structural pathway for the dehydration reactions has been proposed which is consistent with all of these structures and other analytical data obtained. Chapter 4 describes investigations into the structures of a-(Mo02)2P207 by powder diffraction and NMR methods. The high temperature structure was confirmed to be related to a literature model. The low temperature structure was further studied by electron diffraction, second harmonic generation and solid state NMR. The use of these complementary techniques with powder X-ray and neutron diffraction data, led to the solution of the complex superstructure. Chapter 5 describes a study into the structures of (MoO)(_2)P(_4)0(_13). The material undergoes a phase transition at 523 K. The low temperature structure contains 441 unique atoms and as such is the most crystallographically complex oxide solved to date. The high temperature structure contains 253 unique atoms and is the second most complex oxide in the ICSD. Chapter 6 describes the in-situ X-ray studies on the synthesis of M0P(_2)O(_7) from precursors Mo0(_2)(P0(_3))(_2) and (MoO)(_2)P(_4)0(_13) in an H(_2) environment. (Mo0(_2))(_2)P(_2)0(_7) was studied under similar conditions and found to decompose to an unidentifiable poorly crystalline phase. Chapter 7 describes the discovery of a new high temperature synthetic route to cubic ZrMo(_2)0(_8) using extremely rapid time-resolved XRD data recorded at the ESRF. The cubic material forms from its constituent oxides at 1350 K and can be isolated back at room temperature using a quench cooling method. A pure phase sample can be prepared using a Zr0(_2):Mo0(_3) ratio of 1:3. The entire synthesis occurs within seconds and precise control of temperature and time is crucial for this synthesis.