In some embodiments, the present disclosure pertains to methods of mediating a gas evolution reaction by exposing a gas precursor to an electrocatalyst that comprises a plurality of layers with catalytic sites. The exposing results in electrocatalytic conversion of the gas precursor to a gas. Thereafter, the generated gas enhances the electrocatalytic activity of the electrocatalyst by enhancing the accessibility of the catalytic sites to the gas precursor. In some embodiments, the electrocatalyst is associated with an electrically conductive surface (e.g., an electrode) that provides electrical current. In some embodiments, the electrocatalyst is a hydrogen production electrocatalyst that converts H.sup.+ to H.sub.2. In some embodiments, the electrocatalyst includes a transition metal dichalcogenide. Further embodiments of the present disclosure pertain to the aforementioned electrocatalysts for mediating gas evolution reactions.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
 This invention was made with government support under Grant No. OISE-0968405, awarded by the National Science Foundation; Grant No. 12-ERD-053, awarded by the U.S. Department of Energy; and Grant No. DE-AC52-07NA27344, awarded by the U.S. Department of Energy. The government has certain rights in the invention.