Synergizing Fe 2 O 3 Nanoparticles on Single Atom Fe‐N‐C for Nitrate Reduction to Ammonia at Industrial Current Densities

Murphy, Eamonn; Sun, Baiyu; Rüscher, Martina; Liu, Yuanchao; Zang, Wenjie; Guo, Shengyuan; Chen, Yu‐Han; Hejral, Uta; Huang, Ying; Ly, Alvin; Zenyuk, Iryna V.; Pan, Xiaoqing; Timoshenko, Janis; Cuenya, Beatriz Roldán; Spoerke, Erik D.; Atanassov, Plamen

doi:10.1002/adma.202401133

Title: Synergizing Fe ₂ O ₃ Nanoparticles on Single Atom Fe‐N‐C for Nitrate Reduction to Ammonia at Industrial Current Densities

Journal Article · 27 April 2024 · Advanced Materials

DOI: https://doi.org/10.1002/adma.202401133 · OSTI ID:2341638

^[1]; Sun, Baiyu ^[1]; Rüscher, Martina ^[2]; Liu, Yuanchao ^[1]; Zang, Wenjie ^[3]; Guo, Shengyuan ^[1]; Chen, Yu‐Han ^[1]; Hejral, Uta ^[2]; Huang, Ying ^[3]; Ly, Alvin ^[3]; Zenyuk, Iryna V. ^[1]; Pan, Xiaoqing ^[3]; Timoshenko, Janis ^[2]; Cuenya, Beatriz Roldán ^[2]; Spoerke, Erik D. ^[4];

^[1]

Department of Chemical and Biomolecular Engineering National Fuel Cell Research Center University of California Irvine CA 92697 USA
Department of Interface Science Fritz‐Haber‐Institut der Max‐Planck‐Gesellschaft 14195 Berlin Germany
Department of Materials Science and Engineering University of California Irvine CA 92697 USA
Sandia National Laboratories, Energy Storage Technologies &, Systems Albuquerque NM 87185 USA

Abstract The electrochemical reduction of nitrates (NO ₃ ⁻ ) enables a pathway for the carbon neutral synthesis of ammonia (NH ₃ ), via the nitrate reduction reaction (NO ₃ RR), which has been demonstrated at high selectivity. However, to make NH ₃ synthesis cost‐competitive with current technologies, high NH ₃ partial current densities (j _NH3 ) must be achieved to reduce the levelized cost of NH ₃ . Here, the high NO ₃ RR activity of Fe‐based materials is leveraged to synthesize a novel active particle‐active support system with Fe ₂ O ₃ nanoparticles supported on atomically dispersed Fe–N–C. The optimized 3×Fe ₂ O ₃ /Fe–N–C catalyst demonstrates an ultrahigh NO ₃ RR activity, reaching a maximum j _NH3 of 1.95 A cm ⁻² at a Faradaic efficiency (FE) for NH ₃ of 100% and an NH ₃ yield rate over 9 mmol hr ⁻¹ cm ⁻² . Operando XANES and post‐mortem XPS reveal the importance of a pre‐reduction activation step, reducing the surface Fe ₂ O ₃ (Fe ³⁺ ) to highly active Fe ⁰ sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe ₂ O ₃ particles and Fe–N _x sites at highly cathodic potentials, maintaining a current of −1.3 A cm ⁻² over 24 hours. This work exhibits an effective and durable active particle‐active support system enhancing the performance of the NO ₃ RR, enabling industrially relevant current densities and near 100% selectivity.

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Sponsoring Organization:: USDOE

OSTI ID:: 2341638

Alternate ID(s):: OSTI ID: 2341639

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 27 Vol. 36; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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