We are interested in developing colloidal methods for the synthesis of nanostructures with low overpotentials and high activity for multi-electron, multi-proton electrocatalytic reduction reactions. Ligand etching and intercalation will be offered as two complementary methods for dramatically enhancing the catalytic activity of colloidal transition metal dichalcogenide (TMDC) electrocatalysts. A combination of electrical impedance spectroscopy, structural analysis, and electronic structure characterization will be presented to reveal the mechanisms underlying catalytic improvement in these systems. The extension of these and related post-synthetic methods to tune the activity of colloidal transition metal phosphide electrocatalysts will also be discussed.