The development of efficient and robust earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is an ongoing challenge. We report metallic cobalt pyrite (cobalt disulfide, CoS2) as one such high-activity candidate material and demonstrate that its specific morphology--film, microwire, or nanowire, made available through controlled synthesis--plays a crucial role in determining its overall catalytic efficacy. The increase in effective electrode surface area that accompanies CoS2 micro- and nanostructuring substantially boosts its HER catalytic performance, with CoS2 nanowire electrodes achieving geometric current densities of -10 mA cm(-2) at overpotentials as low as -145 mV vs the reversible hydrogen electrode. Moreover, micro- and nanostructuring of the CoS2 material has the synergistic effect of increasing its operational stability, cyclability, and maximum achievable rate of hydrogen generation by promoting the release of evolved gas bubbles from the electrode surface. The benefits of catalyst micro- and nanostructuring are further demonstrated by the increased electrocatalytic activity of CoS2 nanowire electrodes over planar film electrodes toward polysulfide and triiodide reduction, which suggests a straightforward way to improve the performance of quantum dot- and dye-sensitized solar cells, respectively. Extension of this micro- and nanostructuring strategy to other earth-abundant materials could similarly enable inexpensive electrocatalysts that lack the high intrinsic activity of the noble metals.
