Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia
In: Journal of the American Chemical Society, Jg. 145 (2023-10-04), Heft 39, S. 21387-21396
serialPeriodical
Zugriff:
The electrocatalytic nitrate (NO3–) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3−δ(M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3−δ(LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3−δ(LF0.9Cu0.1) submicrofibers with a stronger Fe–O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 μg h–1mg–1cat.and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOLMultiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1submicrofibers can induce NO3–enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situcharacterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton–electron coupling step (*NO3+ H++ e–→ *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.
Titel: |
Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia
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Autor/in / Beteiligte Person: | Chu, Kaibin ; Zong, Wei ; Xue, Guohao ; Guo, Hele ; Qin, Jingjing ; Zhu, Haiyan ; Zhang, Nan ; Tian, Zhihong ; Dong, Hongliang ; Miao, Yue E. ; Roeffaers, Maarten B. J. ; Hofkens, Johan ; Lai, Feili ; Liu, Tianxi |
Link: | |
Zeitschrift: | Journal of the American Chemical Society, Jg. 145 (2023-10-04), Heft 39, S. 21387-21396 |
Veröffentlichung: | 2023 |
Medientyp: | serialPeriodical |
ISSN: | 0002-7863 (print) ; 1520-5126 (print) |
DOI: | 10.1021/jacs.3c06402 |
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