Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters

The limitations of the Haber-Bosch reaction, particularly high-temperature operation, have ignited new interests in low-temperature ammonia-synthesis scenarios. Ambient N-2 electroreduction is a compelling alternative but is impeded by a low ammonia production rate (mostly <10 mmol g(cat)(-1) h(-1)), a small partial current density (<1 mA cm(-2)), and a high-selectivity hydrogen-evolving side reaction. Herein, we report that room-temperature nitrate electroreduction catalyzed by strained ruthenium nanoclusters generates ammonia at a higher rate (5.56 g(cat)(-1) h(-1)) than the Haber- Bosch process. The primary contributor to such performance is hydrogen radicals, which are generated by suppressing hydrogen-hydrogen dimerization during water splitting enabled by the tensile lattice strains. The radicals expedite nitrate-to-ammonia conversion by hydrogenating intermediates of the rate-limiting steps at lower kinetic barriers. The strained nanostructures can maintain nearly 100% ammonia-evolving selectivity at >120 mA cm(-2) current densities for 100 h due to the robust subsurface Ru-O coordination. These findings highlight the potential of nitrate electroreduction in real-world, low-temperature ammonia synthesis.