Achieving a Thermodynamic Self-Regulation Dynamic Adsorption Mechanism for Ammonia Synthesis through Selective Orbital Coupling.

Abstract

With the continuous pursuing on the improvement of catalytic activity, a catalyst performed exceeding catalytic volcano plots is desired, while it is impeded by the adsorption-energy scaling relations of reaction intermediates. Numerous efforts have been focused on optimizing the initial and final intermediates to circumvent the scaling relations for an improved performance. For a step forward, simultaneously optimizing all intermediates is essential to explore the theoretical maximum of catalytic activity. Herein, we proposed a dynamic adsorption mechanism (DAM) to independently regulate the adsorption configurations of all intermediates of electrochemical nitrogen reduction reaction (NRR). To demonstrate the DAM, a multi-site NbNi3 intermetallic is developed, which enables suitable adsorption energies of different intermediates via modulating orbital coupling mechanisms. As a result, NbNi3 achieves an ultra-low limiting potential of NRR of -0.11 V vs. reversible hydrogen electrode (RHE). Strikingly, the theoretical result is confirmed by a proof-of-concept experiment, wherein the nanoporous NbNi3 electrode exhibits a remarkable NH3 yield rate of 25.89 μg h-1 cm-2 with the Faradic efficiency of 33.15% at -0.25 V vs. RHE. Overall, this work brings out a new strategy to avoid the scaling relations, and opens up a promising avenue toward high-efficiency NRR catalysts.