Epitaxially grown silicon-based single-atom catalyst for visible-light-driven syngas production.

Improving the dispersion of active sites simultaneous with the efficient harvest of photons is a key priority for photocatalysis. Crystalline silicon is abundant on Earth and has a suitable bandgap. However, silicon-based photocatalysts combined with metal elements has proved challenging due to silicon's rigid crystal structure and high formation energy. Here we report a solid-state chemistry that produces crystalline silicon with well-dispersed Co atoms. Isolated Co sites in silicon are obtained through the in-situ formation of CoSi 2 intermediate nanodomains that function as seeds, leading to the production of Co-incorporating silicon nanocrystals at the CoSi 2 /Si epitaxial interface. As a result, cobalt-on-silicon single-atom catalysts achieve an external quantum efficiency of 10% for CO 2 -to-syngas conversion, with CO and H 2 yields of 4.7 mol g (Co) -1 and 4.4 mol g (Co) -1 , respectively. Moreover, the H 2 /CO ratio is tunable between 0.8 and 2. This photocatalyst also achieves a corresponding turnover number of 2 × 10 4 for visible-light-driven CO 2 reduction over 6 h, which is over ten times higher than previously reported single-atom photocatalysts.