Activating copper oxide for stable electrocatalytic ammonia oxidation reaction via in-situ introducing oxygen vacancies

Electrocatalytic ammonia oxidation reaction (EAOR) provides an ideal solution for on-board hydrogen supply for fuel cells, while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its practical application. Herein, we reported that the defect engineering via in-situ electrochemically introducing oxygen vacancies (Vo) not only turns the inactive CuO into efficient EAOR catalyst but also achieves a high stability of over 400 h at a high current density of ∼ 200 mA·cm−2. Theoretical simulation reveals that the presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level, which significantly stabilizes the reaction intermediates (⋆NHx) and efficiently oxidizes NH3 into N2. This Vo-modulated CuO shows a different catalytic mechanism from that on the conventional Pt-based catalysts, paving a new avenue to develop inexpensive, efficient, and robust catalysts, not limited to EAOR.