Electrochemical nitrate reduction to ammonia (NRA) provides an efficient, sustainable approach to convert the nitrate pollutants into value-added products, which is regarded as a promising alternative to the industrial Haber-Bosch process. Recent studies have shown that oxygen vacancies of oxide catalysts can adjust the adsorption energies of intermediates and affect their catalytic performance. Compared with other metal oxides, perovskite oxides can allow their metal cations to exist in abnormal or mixed valence states, thereby resulting in enriched oxygen vacancies in their crystal structures. Here, the catalytic activities of perovskite oxides toward NRA catalysis with respect to the amount of oxygen vacancies are explored, where four perovskite oxides with different crystal structures (including cubic LaCrO3 , orthorhombic LaMnO3 and LaFeO3 , hexagonal LaCoO3 ) are chosen and investigated. By combining X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and electrochemical measurements, it is found that the amount of oxygen vacancies in these perovskite oxides surprisingly follow the same order as their activities toward NRA catalysis (LaCrO3 < LaMnO3 < LaFeO3 < LaCoO3 ). Further theoretical studies reveal that the existence of oxygen vacancies in LaCoO3 perovskite can decrease the energy barriers for reduction of *HNO3 to *NO2 , leading to its superior NRA performance.
Keywords: ammonia synthesis; electrocatalysis; nitrate electroreduction; oxygen vacancies; perovskite oxides.
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