N₂-to-NH₃ conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

Ammonia (NH₃) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber-Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N₂ activation barrier and make NH₃ synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N₂-to-NH₃ conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N₂ and H₂ molecules. Herein, we report single-component heterogeneous catalysts based on 5f actinide dioxide surfaces (ThO₂ and UO₂) with oxygen vacancies for N₂-to-NH₃ conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N₂ and H₂ can be activated at different vacancy sites on the same surface; NH₃ is subsequently formed by H^- migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH₃, making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5f actinide dioxide surfaces for N₂ activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH₃ conversion.