Unraveling the Structural Evolution of Cobalt Sulfides in Electrocatalytic NO3RR: the Inescapable Influence of Cl–

Electrochemical nitrate reduction (NO 3 RR) to ammonia is an attractive approach for mitigating NO 3 – pollution and producing valuable NH 3 . Cobalt–sulfur compounds are widely considered to be potential electrocatalysts for NO 3 RR. However, there is still a lack of research on the probable structural evolution, long-term stability, and reactive sites of cobalt-based sulfides during catalysis. Herein, we have employed three cobalt sulfides (CoS x, where x = 8/9, 2, 1.097) with different sulfur contents as catalysts for electrocatalytic NO 3 RR under alkaline conditions. At −0.8 V vs RHE, all these CoS x show promising performances that Faradaic efficiencies of >80% and a high yield of >1780 mmol h –1 g cat –1 for NH 3 production are achieved. Through a combination of X-ray diffraction (XRD), transmission electron microscopy (TEM), and other characterizations, it is revealed that all these cobalt sulfides are easily converted into cobalt hydroxide during the NO 3 RR. This phenomenon is seemingly contradictory to the thermodynamic prediction that, according to the Pourbaix diagram, these CoS x compounds should be stable even under the catalytic condition. We suggest that this is due to the presence of Cl – ions in the electrolyte that promote the transformation of CoS x toward Co(OH) 2 . Chloride ions are commonly found in both industrial settings and natural water bodies and are challenging to remove. The evolved Co(OH) 2 species is proposed to be responsible for catalyzing NO 3 RR, especially during a long-term catalytic process. This study highlights the inevitable structural evolution of CoS x catalysts under current alkaline electrocatalytic NO 3 RR conditions, offering theoretical guidance for the judicious selection and design of future catalysts.