RESUMO
Tailoring nanoscale catalysts to targeted applications is a vital component in reducing the carbon footprint of industrial processes; however, understanding and controlling the nanostructure influence on catalysts is challenging. Molybdenum disulfide (MoS2), a transition metal dichalcogenide (TMD) material, is a popular example of a nonplatinum-group-metal catalyst with tunable nanoscale properties. Doping with transition metal atoms, such as cobalt, is one method of enhancing its catalytic properties. However, the location and influence of dopant atoms on catalyst behavior are poorly understood. To investigate this knowledge gap, we studied the influence of Co dopants in MoS2 nanosheets on catalytic hydrodesulfurization (HDS) through a well-controlled, ligand-directed, tunable colloidal doping approach. X-ray absorption spectroscopy and density functional theory calculations revealed the nonmonotonous relationship between dopant concentration, location, and activity in HDS. Catalyst activity peaked at 21% Co:Mo as Co saturates the edge sites and begins basal plane doping. While Co prefers to dope the edges over basal sites, basal Co atoms are demonstrably more catalytically active than edge Co. These findings provide insight into the hydrogenolysis behavior of doped TMDs and can be extended to other TMD materials.
RESUMO
Magnetic anisotropy critically determines the utility of magnetic nanocrystals (NCs) in new nanomagnetism technologies. Using angular-dependent electron magnetic resonance (EMR), we observe magnetic anisotropy in isotropically arranged NCs of a nonmagnetic material. We show that the shape of the EMR angular variation can be well described by a simple model that considers magnetic dipole-dipole interactions between dipoles randomly located in the NCs, most likely due to surface dangling bonds. The magnetic anisotropy results from the fact that the energy term arising from the magnetic dipole-dipole interactions between all magnetic moments in the system is dominated by only a few dipole pairs, which always have an anisotropic geometric arrangement. Our work shows that magnetic anisotropy may be a general feature of NC systems containing randomly distributed magnetic dipoles.