Single-Layer MoS 2

Single-layer MoS2 is proving to be a versatile material for a wide variety of electronic, optical, and chemical applications. Sulfur depletion, without destabilization of the single layer, is considered a prudent way for making the basal plane of the layer catalytically active. Based on the results of our density-functional-theory examination of vacancy structures on one side of an MoS2 layer, we show that the formation energy per sulfur vacancy is the lowest (energetically favorable) when the vacancies form a row and that the longer the row, the lower the formation energy. In addition, we find that the lowest energy barrier for the diffusion of sulfur vacancy at the row structures through the exchange of a vacancy with a nearby sulfur atom is 0.79 eV and that this barrier increases as the row elongates. We also evaluate the propensity for catalytic activity of an MoS2 layer with two types of sulfur-vacancy structures (row and patch) and find the energetics for alcohol synthesis from syngas to be more favorable for the layer with a sulfur-vacancy patch. © 2014 American Chemical Society

Unraveling the redox behavior of a CoMoS hydrodesulfurization catalyst : A scanning transmission X-ray microscopy study in the tender X-ray range

We visualize the elemental zoning in an alumina-supported cobalt molybdenum sulfide (CoMoS) catalyst with scanning transmission X-ray microscopy (STXM). We use the Canadian Light Source beamline 10-ID's (SM) unique combination of soft X-ray and tender X-ray STXM to determine the spatial variation of Co, Al, Mo, and S species. The results clearly show the correlation between cobalt and molybdenum and the anticorrelation between cobalt and alumina, confirming that Co is closely associated with the MoS2 phase. The tender X-ray STXM images show that the fresh catalyst particle contains a 50 nm ring of molybdenum oxide encapsulating the supported MoS2 phase. After the reduction at 200 °C with H2, this oxide rim disappears and a uniform MoS2 distribution is found. Upon oxidation at 400 °C, the sulfur disappears from the catalyst sample and molybdenum is oxidized from a MoIV sulfide to a mainly tetrahedral MoVI oxide, while cobalt keeps its divalent nature and changes from a CoII sulfide to a CoII oxide