In Situ Formation of Li₂SiO₃-Li-NaCl Interface on Si and Its Effect on Hydrogen Evolution

Silicon has emerged as a competitive candidate for hydrolytic hydrogen production due to its high theoretical hydrogen yield, low cost, and on-demand availability. However, the hydrolysis reaction is extremely restrained by passivated SiO 2, including the original one on the Si surface and the generated one during hydrolysis, and almost no hydrogen is produced in pure water. Herein, the original SiO 2 surface has been effectively removed by milling micro-Si mixed with a small amount of Li metal and NaCl. An artificial soluble interface on Si has been established containing Li 2 SiO 3, Li, and NaCl. Once micro-Si is placed into water, fresh Si surface can be exposed and a weak LiOH solution can be generated due to the fast dissolution of the interface layer, resulting in the rapid liberation of hydrogen gas. Accordingly, the modified micro-Si displays a significantly enhanced hydrogen production in pure water at 30 °C (1213 mL g –1 H 2 within 3.0 h), which is 2.0 and 4.7 times higher than that observed for ball-milled Si and raw Si in 0.06 M LiOH solution, respectively. In addition, it also exhibited an outstanding operation compatibility for practical uses. This work has proposed a green, effective, and scalable strategy to promote hydrogen production from the hydrolysis of Si-based systems.