Role of Structural and Compositional Changes of Cu₂O Nanocubes in Nitrate Electroreduction to Ammonia

High Resolution Image Download MS PowerPoint Slide Nitrate electroreduction reaction (NO 3 RR) to ammonia (NH 3 ) still faces fundamental and technological challenges. While Cu-based catalysts have been widely explored, their activity and stability relationship are still not fully understood. Here, we systematically monitored the dynamic alterations in the chemical and morphological characteristics of Cu 2 O nanocubes (NCs) during NO 3 RR in an alkaline electrolyte. In 1 h of electrolysis from −0.10 to −0.60 V vs RHE, the electrocatalyst achieved the maximum NH 3 faradaic efficiency (FE) and yield rate at −0.3 V (94% and 149 μmol h –1 cm –2, respectively). Similar efficiency could be found at a lower overpotential (−0.20 V vs RHE) in long-term electrolysis. At −0.20 V vs RHE, the catalyst FE increased from 73% in the first 2 h to ∼90% in 10 h of electrolysis. Electron microscopy revealed the loss of the cubic shape with the formation of sintered domains. In situ Raman, X-ray diffraction (XRD), and in situ Cu K-edge X-ray absorption near-edge spectroscopy (XANES) indicated the reduction of Cu 2 O to oxide-derived Cu 0 (OD-Cu). Nevertheless, a remaining Cu 2 O phase was noticed after 1 h of electrolysis at −0.3 V vs RHE. This observation indicates that the activity and selectivity of the initially well-defined Cu 2 O NCs are not solely dependent on the initial structure. Instead, it underscores the emergence of an OD-Cu-rich surface, evolving from near-surface to underlying layers over time and playing a crucial role in the reaction pathways. By employing online differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR), we experimentally probed the presence of key intermediates (NO and NH 2 OH) and byproducts of NO 3 RR (N 2 and N 2 H x ) for NH 3 formation. These results show a complex relationship between activity and stability of the nanostructured Cu 2 O oxide catalyst for NO 3 RR.