TY - JOUR
T1 - Synthesis of ternary sulfide nanomaterials using dithiocarbamate complexes as single source precursors
AU - Roffey, Anna
AU - Hollingsworth, Nathan
AU - Hogarth, Graeme
PY - 2019/1/1
Y1 - 2019/1/1
N2 - We report the use of cheap, readily accessible and easy to handle di-isobutyl-dithiocarbamate complexes, [M(S2CNiBu2)n], as single source precursors (SSPs) to ternary sulfides of iron-nickel, iron-copper and nickel-cobalt. Varying decomposition temperature and precursor concentrations has a significant effect on both the phase and size of the nanomaterials, and in some instances meta-stable phases are accessible. Decomposition of [Fe(S2CNiBu2)3]/[Ni(S2CNiBu2)2] at ca. 210-230 °C affords metastable FeNi2S4 (violarite) nanoparticles, while at higher temperatures the thermodynamic product (Fe,Ni)9S8 (pentlandite) results. Addition of tetra-isobutyl-thiuram disulfide to the decomposition mixture can significantly affect the nature of the product at any particular temperature-concentration, being attributed to suppression of the intramolecular Fe(iii) to Fe(ii) reduction. Attempts to replicate this simple approach to ternary metal sulfides of iron-indium and iron-zinc were unsuccessful, mixtures of binary metal sulfides resulting. Oleylamine is non-innocent in these transformations, and we propose that SSP decomposition occurs via primary-secondary backbone amide-exchange with primary dithiocarbamate complexes, [M(S2CNHoleyl)n], being the active decomposition precursors.
AB - We report the use of cheap, readily accessible and easy to handle di-isobutyl-dithiocarbamate complexes, [M(S2CNiBu2)n], as single source precursors (SSPs) to ternary sulfides of iron-nickel, iron-copper and nickel-cobalt. Varying decomposition temperature and precursor concentrations has a significant effect on both the phase and size of the nanomaterials, and in some instances meta-stable phases are accessible. Decomposition of [Fe(S2CNiBu2)3]/[Ni(S2CNiBu2)2] at ca. 210-230 °C affords metastable FeNi2S4 (violarite) nanoparticles, while at higher temperatures the thermodynamic product (Fe,Ni)9S8 (pentlandite) results. Addition of tetra-isobutyl-thiuram disulfide to the decomposition mixture can significantly affect the nature of the product at any particular temperature-concentration, being attributed to suppression of the intramolecular Fe(iii) to Fe(ii) reduction. Attempts to replicate this simple approach to ternary metal sulfides of iron-indium and iron-zinc were unsuccessful, mixtures of binary metal sulfides resulting. Oleylamine is non-innocent in these transformations, and we propose that SSP decomposition occurs via primary-secondary backbone amide-exchange with primary dithiocarbamate complexes, [M(S2CNHoleyl)n], being the active decomposition precursors.
UR - http://www.scopus.com/inward/record.url?scp=85072017754&partnerID=8YFLogxK
U2 - 10.1039/c9na00275h
DO - 10.1039/c9na00275h
M3 - Article
AN - SCOPUS:85072017754
SN - 2516-0230
VL - 1
SP - 3056
EP - 3066
JO - Nanoscale Advances
JF - Nanoscale Advances
IS - 8
ER -