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Updated: Jun 14, 2025

Ammonia Synthesis at Low Pressure
Published on: August 23, 2017
Silicon Clathrate-Supported Catalysts with Low Work Functions for Ammonia Synthesis
Walid Al Maksoud1, Raza Ullah Shah Bacha1, Jan-Malte Pixius1,2
1KAUST Catalysis Center, and Center for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
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 AxSi46 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 K8Si46 to be effective Haber-Bosch catalyst supports for NH3 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.
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