Breaking the Volcano-Shaped Relationship for Highly Efficient Electrocatalytic Nitrogen Reduction: A Computational Guideline

The volcano-shaped relationship is very common in electrocatalytic nitrogen reduction reaction (e-NRR) and is usually caused by the competition between the first and last hydrogenation steps. How to break such a relationship to further improve the catalytic performance remains a great challenge. Herein, using first-principles calculations, we investigate a range of transition-metal (TM)-doped Cu-based single-atom alloys (TM1-Cu(111)) as catalysts for e-NRR. When the adsorption of N2 on the catalysts is strong enough, the inert N2 molecules can be effectively activated for the first hydrogenation step. Meanwhile, the last hydrogenation step is not affected by the scaling relationship and remains easy on all of the catalysts due to the unstable top-site adsorption of NH2, resulting in the break of the volcano-shaped relationship in e-NRR. Thus, only the first hydrogenation step is identified as the potential determining step. Four TM1-Cu(111) catalysts (TM = Re, W, Tc, and Mo) are selected as promising catalysts with limiting potential ranging from −0.38 to −0.56 V, showing outstanding e-NRR activity. Besides, the four catalysts also inhibit the competing hydrogen evolution reaction and long-term stability. Our work provides a guideline for breaking the volcano-shaped relationship in e-NRR and significant in the rational design of highly efficient electrocatalysts.