Structural dependence of intermediate species for the hydrogen evolution reaction on single crystal electrodes of Pt

► The structural dependence of intermediate H on Pt during the hydrogen evolution reaction (HER) has been studied using infrared spectroscopy. ► The atop H was observed on Pt(110) and the several stepped surface with (110) step. ► The asymmetric bridge H appears on Pt(100) and the surfaces with (100) step. ► The symmetric bridge site on Pt(100) and Pt(211) strongly stabilizes Had.