Mechanism of sulfidation of small zinc oxide nanoparticles.

ZnO has industrial utility as a solid sorbent for the removal of polluting sulfur compounds from petroleum-based fuels. Small ZnO nanoparticles may be more effective in terms of sorption capacity and ease of sulfidation as compared to bulk ZnO. Motivated by this promise, here, we study the sulfidation of ZnO NPs and uncover the solid-state mechanism of the process by crystallographic and optical absorbance characterization. The wurtzite-structure ZnO NPs undergo complete sulfidation to yield ZnS NPs with a drastically different zincblende structure. However, in the early stages, the ZnO NP lattice undergoes only substitutional doping by sulfur, while retaining its wurtzite structure. Above a threshold sulfur-doping level of 30 mol%, separate zincblende ZnS grains nucleate, which grow at the expense of the ZnO NPs, finally yielding ZnS NPs. Thus, the full oxide to sulfide transformation cannot be viewed simply as a topotactic place-exchange of anions. The product ZnS NPs formed by nucleation-growth share neither the crystallographic structure nor the size of the initial ZnO NPs. The reaction mechanism may inform the future design of nanostructured ZnO sorbents.