Non-noble single-atom alloy for electrocatalytic nitrate reduction using hierarchical high-throughput screening

Electrochemical nitrate reduction reaction (NO3RR) holds promise for the management of wastewater contamination and synthesis of carbon-neutral ammonia (NH3). However, high-quality catalysts with controllable reaction pathways and high activity and selectivity are still lacking. The emerging single atom alloys (SAAs) offer attractive possibilities in nitrate reduction due to their unique atomic and electronic structures. By high-throughput first-principles calculations, we explore the possible incorporation of a series of transition-metal alloyed Cu-based SAAs, referred to as TM/Cu(111), for NO3RR toward NH3. A hierarchical four-step screening strategy have been employed to evaluate twenty-seven SAA catalysts yielding three alloying elements (Ti, Ni and Nb) with high catalytic activity and NO3RR selectivity. Finally, only Ni/Cu(111) possess the best activity among these three candidates because of its lowest limiting potential of - 0.29 V. After further analysis, we found that the adsorption free energy of *NO3 can be recognized as efficient descriptor to design and predict the NO3RR performance of SAA. Furthermore, the Cu-based SAAs were revealed to exhibit pH dependent properties, which influence the competition between the hydrogen evolution reaction (HER) and NO3RR. This work not only indicates the significant potential of SAA in electrocatalysis for NO3RR to NH3, but also highlights the important influence of pH on the activity and selectivity of catalysts under reaction conditions.

Automated summary

Electrochemical nitrate reduction reaction (NO3RR) has potential in wastewater management and carbon-neutral ammonia synthesis, but lacks high-quality catalysts with controllable reaction pathways and high activity and selectivity. In this study, we explore the application of single atom alloys (SAAs) in nitrate reduction through high-throughput first-principles calculations. We identify Ni/Cu(111) as the most active SAA catalyst for NO3RR and find that the adsorption free energy of *NO3 can serve as an efficient descriptor to design and predict the NO3RR performance of SAAs. Furthermore, we reveal the pH-dependent properties of Cu-based SAAs, which influence the competition between the hydrogen evolution reaction (HER) and NO3RR.