The n-Si(111)76 M KOH electrolyte interface has been investigated by in-situ multiple-internal reflection infrared spectroscopy, at room temperature and at40 degrees C. The potential of the Si electrode was stepped successively to positive and negative values with respect to open-circuit potential, leading to surface oxidation and oxide dissolution, respectively. Infrared spectra were recorded together with the interfacial current. Analysis of the infrared spectra indicates that, following the positive potential step, the electronic state of the surface changes from accumulation to inversion and the surface termination changes from a hydrogenated state to an oxidised state. The hydrogenated state is recovered after an induction time following the negative potential step. However, hydrogen penetration into the silicon lattice is then found to take place, as indicated by the appearance of a new SiH band and a strong background absorption of electronic origin. This sub-surface hydrogenation is associated with a slow increase of the interfacial current This process is found to be especially important at higher temperature and is attributed to the formation of microcracks partially decorated with hydrogen. These results indicate that the chemistry and morphology of a silicon electrode are not stable even in the presence of an applied negative potential. (C) 2015 Elsevier B.V. All rights reserved.