Mixed metal alkoxides as ascatalyst precursors

Abstract

This thesis describes research carried out to explore the use of mixed metal alkoxides as precursors of materials with catalytic activity in synthesis-gas chemistry. The alkoxide derived catalyst materials are compared against catalysts prepared by traditional co-precipitation methods. A discussion of the project objectives introduces the work and Chapter 1 includes a chronological survey of the literature up to the present day. A brief discussion of the commercial uses of alkoxides is given. Chapter 2 describes the general methods of synthesis and the properties of simple and bimetallic alkoxides; M(OR)(_x) and M[M'(OR)(_n)](_x) respectively. A more detailed treatment of the alkoxides of the first row transition elements is given, with emphasis on the properties and characteristics responsible for their possible potential as catalyst precursors. Chapter 3 deals with the catalytic aspects of ammonia and methanol synthesis. The preparation of industrial, heterogeneous catalysts has traditionally been carried out by co-precipitation of, for example, basic carbonates. The catalytic materials obtained may display catalytic activities which vary markedly (and not always controllably) with the precipitation, ageing, calcinations and/or reduction conditions employed. A discussion of the reaction mechanisms involved in ammonia and methanol syntheses is included. Several mixed metal alkoxides have been prepared from metals known to have catalytic activity in synthesis-gas chemistry (i.e. Mn, Fe, Co, Cu, Zn and Al). These metal alkoxides (e.g. Cu[Al(OPr(^1) (_4)](_2) ) have been characterised and found to compare well with literature data. Analyses, Infra-red and Mass-spectra are reported. After conversion to catalytic materials the alkoxide derived compounds were examined for surface properties ( oxide phases present, copper surface area, crystallite size, pore size distributions and pore volumes). The alkoxide materials compared quite well with the precipitated analogues and there was a difference in the properties of materials derived from different alkoxy groups. These studies were limited to the copper-aluminium alkoxides. The formation of a nickel (II) chloride, HMPA adduct is reported.