Electrocatalytic Nitrate and Nitrite Reduction toward Ammonia Using Cu 2 O Nanocubes: Active Species and Reaction Mechanisms.

Autor:	Bai L; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Franco F; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Timoshenko J; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Rettenmaier C; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Scholten F; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Jeon HS; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Yoon A; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Rüscher M; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Herzog A; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Haase FT; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Kühl S; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Chee SW; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Bergmann A; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany., Beatriz RC; Department of Interface Science, Fritz-Haber-Institute of Max-Planck-Society, Faradayweg 4-6, 14195 Berlin, Germany.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2024 Apr 10; Vol. 146 (14), pp. 9665-9678. Date of Electronic Publication: 2024 Apr 01.
DOI:	10.1021/jacs.3c13288
Abstrakt:	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.
Databáze:	MEDLINE
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