Atomic-Scale Mechanism of Efficient Hydrogen Evolution at SiC Nanocrystal Electrodes

Efficient electrochemical hydrogen evolution at ultrathin 3C-SiC nanocrystal electrodes in acid solutions was recently reported, but the atomic-scale mechanism of the reaction was not identified. Here we report quantum mechanical calculations of pertinent reactions and show that the reaction happens at pre-existing hydrogenated surface Si-H sites through a mechanism that is related to the Volmer-Heyrovsky mechanism that occurs in metals. Here the Heyrovsky reaction occurs as the first step, where an electron from the substrate reacts with a hydronium adsorbed at a Si-H site, creating an H-2 molecule and a Si dangling bond. The Volmer reaction follows and regenerates the Si-H. This ordering of reactions is supported by the fact that the hydrogen coverage on SiC electrodes does not depend on the applied voltage, in contrast to the cases of metal electrodes. Moreover, the Volmer reaction, which is a one-step process on metal surface, is a two-step process here. We then show that the rise of the conduction band due to quantum confinement accounts for the fact that only ultrasmall SiC nanocrystals are electrochemically active. We also show that the ability of a Si-H bond to bind a hydronium is essential for the hydrogen evolution to occur at high rate.