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Electron and Hydrogen Dual Spillover at CeO2/Fe3C Interfaces for Efficient NH3 Electrosynthesis and High-Performance
Jiaqi Huang1, Deng Liu1, Dong Lv1
1Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai, People's Republic of China.
Abstract:
The electrocatalytic nitrate reduction reaction (NO3RR) offers a sustainable route for ambient ammonia synthesis but is hindered by insufficient active hydrogen (*H) supply and strong adsorption of oxygen-containing intermediates. Herein, we propose an electron- and hydrogen-dual-channel interfacial engineering strategy by constructing a heterojunction of grain-boundary-rich CeO2 intimately interfaced with Fe3C on nickel foam (CeO2/Fe3C@NF). Oxygen-vacancy-rich CeO2 with reversible Ce3+/Ce4+ redox pairs serves a dual function: it donates electrons to Fe3C, downshifting the d-band center of Fe sites to weaken intermediate adsorption and mitigate surface poisoning; and it facilitates water dissociation to generate *H, which spills over onto Fe3C to ensure adequate *H supply for hydrogenation. Benefiting from this dual spillover mechanism, CeO2/Fe3C@NF achieves an exceptional NH3 electrosynthesis rate of 1.343 mmol h-1 cm-2 with a Faradaic efficiency of 97.04% at -0.3 V vs. RHE in an H-type cell, ranking among the best non-precious NO3RR electrocatalysts. Furthermore, a rechargeable Zn-NO3 - battery using CeO2/Fe3C@NF as the cathode delivers a power density of 8.93 mW cm-2 and stable operation over 100 h. This work establishes an electron- and hydrogen-dual-channel paradigm for rational design of efficient NO3RR electrocatalysts.
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