▎ 摘　　要

The production of hydrogen via water electrolysis using renewable electricity is a promising carbon-neutral technology. In this contribution, we report insights into the hydrogen evolution reaction (HER) in H2SO4 on Pt(111) and graphene-covered Pt(111), in addition to the electrochemical properties of graphene overlayers. As-prepared graphene overlayers are selectively permeable to H+ ions in the electrolyte, allowing H+ ions into the confined layer between graphene and Pt(111) while excluding SO42- and other anions. We demonstrate that defects in these as-prepared graphene overlayers can be generated from oxidation at high overpotentials or reduction from the production of H-2 bubbles and postulate that HER occurs locally at only Pt(111) in the proximity of defects in graphene overlayers on asprepared G/Pt(111) electrodes, and as defects in graphene increases, more of the Pt(111) surface becomes utilized for HER. Kinetically, the addition of defective graphene overlayers can increase the geometric HER rate by up to 200%, while Tafel slopes and [H+] reaction orders remain unchanged. These results shed kinetic insight into the nature of graphene overlayers and their effect on HER catalysis and also demonstrate the promise of confinement modifications in designing catalysts with properties closer to achieving optimum rates.