Efficient nitrate electroreduction to ammonia via synergistic cascade catalysis at Cu/Fe2O3 hetero-interfaces

doi:10.1016/S1872-2067(24)60194-4

Abstract

Abstract:

Electrochemical nitrate (NO₃⁻) reduction offers a promising route for ammonia (NH₃) synthesis from industrial wastewater using renewable energy. However, achieving selective and active NO₃⁻ to NH₃ conversion at low potentials remains challenging due to complex multi-electron transfer processes and competing reactions. Herein, we tackle this challenge by developing a cascade catalysis approach using synergistic active sites at Cu-Fe₂O₃ interfaces, significantly reducing the NO₃⁻ to NH₃ at a low onset potential to about +0.4 V_RHE. Specifically, Cu optimizes *NO₃ adsorption, facilitating NO₃⁻ to nitrite (NO₂⁻) conversion, while adjacent Fe species in Fe₂O₃ promote the subsequent NO₂⁻ reduction to NH₃ with favorable *NO₂ adsorption. Electrochemical operating experiments, in situ Raman spectroscopy, and in situ infrared spectroscopy consolidate this improved onset potential and reduction kinetics via cascade catalysis. An NH₃ partial current density of ~423 mA cm⁻² and an NH₃ Faradaic efficiency (FE_NH3) of 99.4% were achieved at −0.6 V_RHE, with a maximum NH₃ production rate of 2.71 mmol h⁻¹ cm⁻² at −0.8 V_RHE. Remarkably, the half-cell energy efficiency exceeded 35% at −0.27 V_RHE (80% iR corrected), maintaining an FE_NH3 above 90% across a wide range of NO₃⁻ concentrations (0.05−1 mol L⁻¹). Using ¹⁵N isotopic tracing, we confirmed NO₃⁻ as the sole nitrogen source and attained a 98% NO₃⁻ removal efficiency. The catalyst exhibit stability over 106-h of continuous operation without noticeable degradation. This work highlights distinctive active sites in Cu-Fe₂O₃ for promoting the cascade NO₃⁻ to NO₂⁻ and NO₂⁻ to NH₃ electrolysis at industrial relevant current densities.

Key words: Electrocatalysis, Reaction onset potential, Nitrate reduction to ammonia, Cascade catalysis, Heterogeneous interface

Xiang Zhang, Weihang Li, Jin Zhang, Haoshen Zhou, Miao Zhong. Efficient nitrate electroreduction to ammonia via synergistic cascade catalysis at Cu/Fe₂O₃ hetero-interfaces[J]. Chinese Journal of Catalysis, 2025, 68: 404-413.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60194-4

https://www.cjcatal.com/EN/Y2025/V68/I1/404

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the cascade catalysis of NO3? electroreduction to NH3 on the Cu-Fe2O3 electrode. (b) LSV curves comparing Cu-Fe2O3, Cu, and Fe2O3 deposited on Ni foam in 1 mol L?1 KOH with 0.1 mol L?1 KNO3 (solid line) and without KNO3 (dashed line) at a scan rate of 5 mV s?1 (80% iR corrected). The orange line indicates a current density of 10 mA cm?2. (c) LSV curve at +0.1 to +0.4 VRHE. The gray line indicates the cathodic current density of 1 mA cm?2.

Fig. 2. Electrochemical analysis of NO3?RR using Cu-Fe2O3, Cu, and Fe2O3 catalysts loaded on Ni foams. LSV curves of Cu (a), Fe2O3 (b), and Cu-Fe2O3 (c) catalysts on Ni foams in 1 mol L?1 KOH and 0.1 mol L?1 KNO3 (80% iR corrected). (d) Tafel slopes of Cu, Fe2O3, and Cu-Fe2O3 catalysts on Ni foams in 1 mol L?1 KOH and 0.1 mol L?1 KNO3. FE (e) and yield rate (f) of NH3 for the catalysts at different potentials. (g) Partial current densities of NH3 (80% iR corrected) at different potentials with different catalysts. (h) EE of NH3 (80% iR corrected) with different catalysts. (i) FE and yield rate of NH3 for catalysts with different valence states of Fe species combined with Cu at ?0.6 VRHE.

Fig. 3. In situ Raman spectra at various potentials of Cu-Fe2O3 (a), Cu (b), and Fe2O3 (c). (d) In situ FTIR spectroscopy of Cu-Fe2O3 in 1 mol L?1 KOH and 0.1 mol L?1 KNO3.

Fig. 4. Electrochemical NO3?RR performance on Cu-Fe2O3 electrodes. (a) UV-vis absorption spectra of the electrolytes after the reduction reaction in 1 mol L?1 KOH with and without 0.1 mol L?1 KNO3 at ?0.6 VRHE and at OCP. The electrolyte was diluted to 500 times in volume before measurement. (b) 1H-NMR spectra of the NO3?RR electrolyte using K14NO3 and K15NO3 as the N source in 1 mol L?1 KOH electrolyte at ?0.6 VRHE. The reduction reaction was performed for 1 h. (c) NH3 yield rates at ?0.6 VRHE, measured using Nessler's reagent method and 1H-NMR spectroscopy. (d) LSV curves of Cu-Fe2O3 electrodes with different KNO3 concentrations in 1 mol L?1 KOH (80% iR corrected). (e) NH3 FE and yield rate of Cu-Fe2O3 at ?0.6 VRHE. (f) The time-dependent concentrations of NO3?, NO2? and NH3 and the corresponding FE during the NO3?RR process on Cu-Fe2O3 at ?0.6 VRHE. (g) The time-dependent concentrations of NO3?, NO2? and NH3 during the NO3?RR process using Cu-Fe2O3 at ?0.6 VRHE. (h) NO3?RR durability test using Cu-Fe2O3 at ?400 mA cm?2 in 1 mol L?1 KOH + 1 mol L?1 KNO3.

Fig. 5. Structure and composition characterization of the Cu-Fe2O3 catalyst after the 1-h NO3?RR. (a) SEM images of the Cu-Fe2O3 catalyst. (b-d) HRTEM images and the corresponding EDX elemental mapping images of Cu-Fe2O3. Fe 2p (e) and Cu 2p (f) narrow-scan XPS spectra of Cu-Fe2O3. (g) XRD patterns of Cu-Fe2O3, Cu, and Fe2O3 loaded on Ni foam.

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Efficient nitrate electroreduction to ammonia via synergistic cascade catalysis at Cu/Fe₂O₃ hetero-interfaces

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