2024/04/01 by Lichen Bai, Federico Franco, Janis Timoshenko +11 · 3 citations
Chemical Engineering · Computer Science · Energy · #Ammonia Synthesis and Nitrogen Reduction #Caching and Content Delivery #Advanced Photocatalysis Techniques
paper · pdf · doi:10.1021/jacs.3c13288
openalex publication_date 2024/04/01 · openalex created_date 2024/04/02 · openalex updated_date 2026/07/29
High Resolution Image Download MS PowerPoint Slide The electrochemical reduction of nitrate (NO 3 – ) and nitrite (NO 2 – ) enables sustainable, carbon-neutral, and decentralized routes to produce ammonia (NH 3 ). Copper-based materials are promising electrocatalysts for NO x – conversion to NH 3 . However, the underlying reaction mechanisms and the role of different Cu species during the catalytic process are still poorly understood. Herein, by combining quasi in situ X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption spectroscopy (XAS), we unveiled that Cu is mostly in metallic form during the highly selective reduction of NO 3 – /NO 2 – to NH 3 . On the contrary, Cu(I) species are predominant in a potential region where the two-electron reduction of NO 3 – to NO 2 – is the major reaction. Electrokinetic analysis and in situ Raman spectroscopy was also used to propose possible steps and intermediates leading to NO 2 – and NH 3, respectively. This work establishes a correlation between the catalytic performance and the dynamic changes of the chemical state of Cu, and provides crucial mechanistic insights into the pathways for NO 3 – /NO 2 – electrocatalytic reduction.