Silicon Clathrate‐Supported Catalysts with Low Work Functions for Ammonia Synthesis

Abstract Diamond‐type silicon has a work function of ≈4.8 eV, and conventional n‐ or p‐type doping modifies the value only between 4.6 and 5.05 eV. Here, it is shown that the alkali clathrates A x Si 46 have substantially lower work functions approaching 2.6 eV, with clear trends between alkali electropositivity and clathrate cage size. The low work function enables alkali clathrates such as K 8 Si 46 to be effective Haber‐Bosch catalyst supports for NH 3 synthesis. The catalytic properties of Si, Ge, and Sn‐based clathrates are investigated while supporting Fe and Ru on the surface. The activity largely scales with the work function, and low activation energies below 60 kJ mol −1 are observed due to strong electron donation effects from the support. Ru metal and Sn clathrates seem to be unsuitable for stability issues. Compared to other similar hydride/electride catalysts, the simple structure and composition combined with stability in air/water make a systematic study of these clathrates possible and open the door to other electron‐rich Zintl phases and related intermetallics as low‐work function materials suitable for catalysis. The observed low work function may also have implications for other existing electronic applications.