Photocatalytic hydrogen generation using mesoporous silicon nanoparticles: influence of magnesiothermic reduction conditions and nanoparticle aging on the catalytic activity.

In recent years, mesoporous silicon (mp-Si) nanoparticles (NPs) have been recognized as promising materials for sustainable photocatalytic hydrogen (H2) generation, which is both an important chemical feedstock and potential clean energy vector. These materials are commonly prepared via magnesiothermic reduction of silica precursors due to the ease, scalability, and tunability of this reaction. In this work, we investigate how the conditions of magnesiothermic reduction (i.e. reaction temperature and time) influence the performance of mp-Si for photocatalytic H2 generation. The mp-Si NPs were prepared using either the conventional single temperature heating method (650 °C for 3 or 6 h) or a two-temperature method in which the reaction is initially heated to 650 °C for 0.5 h, followed by a second step heating at 100 (mp-Si100), 200 (mp-Si200), or 300 °C (mp-Si300) for 6 h. Of these, mp-Si300 was the best performing photocatalyst and showed the highest H2 evolution rate (4437 μmol h-1 g-1 Si). Our results suggest that crystallinity has a profound effect on the performance of mp-Si photocatalysts. Additionally, high amounts of oxygen and particle sintering lower H2 evolution rates by introducing defect states or grain boundaries. It was also discovered that aging mp-Si NPs under ambient conditions result in continued surface oxidation which deleteriously affects its photocatalytic performance.