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Updated: Jan 24, 2026

Ammonia Synthesis at Low Pressure
Published on: August 23, 2017
Cooperation of Carboxylate and Sulfonate Ligands in a High-Efficiency Ru Catalyst for Electrocatalytic Ammonia
Huatian Xiong1, Jia-Yi Chen2, Jing Yang3
1Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310024, Zhejiang, China.
Abstract:
The development of efficient electrocatalysts for ammonia oxidation is crucial for utilizing ammonia as a fuel. Herein, by employing a hybrid bipyridine-carboxylate-sulfonate ligand, we successfully optimized the primary and secondary coordination spheres of a Ru-based ammonia oxidation catalyst. The resulting [Ru(bcs-κ3O,N,N)(Py)2(NH3)] (Ru-bcs-NH3; bcs = 2,2'-bipyridine-6-carboxylate-6'-sulfonate; Py = pyridine) catalyst achieves a record turnover number (TON = 1.2 × 104, after heterogenization) and catalytic rate (kobs = 230 s-1) among reported molecular systems in organic phase. Compared with the analogues Ru-bds-NH3 (bds = 2,2'-bipyridine-6,6'-disulfonate) and Ru-bda-NH3 (bda = 2,2'-bipyridine-6,6'-dicarboxylate), we revealed the division of labor between carboxylate and sulfonate groups during ammonia oxidation by Ru-bcs-NH3: the coordinated carboxylate provides strong electron donation to lower the redox potential and the energy barrier of the rate-determining step, while the dangling sulfonate group enables efficient proton shuttling without competing with the key active site. This work establishes ruthenium complexes with bifunctional ligand environments as promising molecular platforms for the efficient conversion of ammonia to nitrogen.
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