Dithiocarbamate Complexes as Single Source Precursors to Metal Sulfide Nanoparticles for Applications in Catalysis

Herein we report the solvothermal decomposition of a range of metal dithiocarbamate complexes for the synthesis of metal sulfide nanoparticles. Metal sulfides exist in a variety of structural phases, some of which are known to be catalytically active towards various processes. The aim of this work was to synthesise a variety of different metal sulfide phases for future catalysis testing, particularly the iron sulfide greigite (Fe3S4, a thiospinel containing Fe2+ and Fe3+) which is to be tested for CO2 reduction. A range of metal dithiocarbamate complexes were synthesised and Chapter 2 focusses on the synthesis of iron dithiocarbamates. Both iron(II) and iron(III) complexes were synthesised, the latter being a facile, open bench reaction producing a range of [Fe(S2CNRR’)3] complexes. Iron(II) bis(dithiocarbamates) are extremely air sensitive therefore carbonyl protected [Fe(S2CNRR’)2(CO)2] complexes were prepared for ease of use as precursors. The stability of the complexes was tested by TGA to ensure they were suitable precursors for metal sulfide synthesis, i.e. that the carbonyl ligands were sufficiently labile to leave the complexes before decomposition, which proved to be successful. In the following Chapter these iron dithiocarbamate complexes were solvothermally decomposed, but interestingly a combination of iron(II) and iron(III) precursors did not produce greigite as expected, but pyrrhotite (Fe7S8, containing only Fe2+). Systematic studies into the effect of decomposition temperature, precursor concentration and precursor type, on the phase and morphology of the resulting iron sulfide nanoparticles were performed on the iron(III) dithiocarbamate precursor. The phase was found to be highly dependent on both concentration and temperature. The use of a redox active additive, thiuram disulfide, on the decomposition was also investigated and found to have a significant effect, promoting the formation of the metastable greigite phase. Chapter 4 examines the nickel bis(dithiocarbamate) decomposition system to see if its behaviour was consistent with trends observed in the iron case. In general, similar trends were observed in the phase and morphology of the nickel sulfides when the decomposition parameters were varied, metastable phases were observed at lower temperature and higher concentration. The effect of thiuram disulfide on the system was greater, however, than in the iron case, whereby an additional nickel sulfide phase (NiS2) was observed at high concentration in the presence of this additive. Chapter 5 deals with a broader range of metal dithiocarbamate systems, to attempt to elucidate whether or not the trends seen for nickel and iron are universal for metal dithiocarbamate precursors. The Co, Cu, Zn and In dithiocarbamate systems were examined with and without thiuram disulfide, and some effect were seen on the phase of metal sulfide nanoparticle formed, but only at high concentration in the presence of the additive. Mixed-metal studies were performed to investigate the suitability of metal dithiocarbamates as precursors to ternary metal sulfides, and success was observed for iron-nickel, cobalt-nickel and iron-copper sulfides, though the iron-zinc and iron-indium systems only produced binary sulfides. The final Chapter looks into the metal dithiocarbamate decomposition mechanism in detail, using [Ni(S2CNiBu2)2] as a model system. NMR, in situ UV-vis, MS and powder XRD are all employed to probe the mechanism, in conjunction with XAS and computer modelling which was performed by others. The mechanism was found to rely heavily on an intermediate formed from amide exchange between the dithiocarbamate backbone and solvent amine, indicating the solvent plays an extremely significant role in the solvothermal synthesis of metal sulfides from dithiocarbamate precursors.