Magnetic Moment Is an Effective Descriptor for Electrocatalytic Nitrogen Reduction Reaction on Two-Dimensional Organometallic Nanosheets

Electrocatalytic reduction of nitrogen to ammonia (eNRR) under ambient condition is a potential sustainable and promising alternative to the traditional Haber–Bosch process. However, this electrochemical transformation is limited by the high overpotential, poor selectivity, low efficiency, and low yield. Herein, a new class of two-dimensional (2D) organometallic nanosheets c-TM-TCNE (c = cross motif, TM = 3d/4d/5d transition metals, TCNE = tetracyanoethylene) were comprehensively investigated as potential electrocatalysts for eNRR through high-throughput screening combined with spin-polarized density functional theory computations. After a multistep screening and follow-up systematic evaluation, c-Mo-TCNE and c-Nb-TCNE were selected as eligible catalysts, and c-Mo-TCNE showed the lowest limiting potential of −0.35 V via a distal pathway, displaying high catalytic performance. In addition, the desorption of NH 3 from the surface of c-Mo-TCNE catalyst is also easy, with the free energy being 0.34 eV. Furthermore, the stability, metallicity, and eNRR selectivity are preeminent, making c-Mo-TCNE a promising catalyst. Unexpectedly, the magnetic moment of the transition metal shows a strong correlation with the catalytic activity (limiting potential), i.e., the larger the magnetic moment of the transition metal, the smaller the limiting potential of the electrocatalyst. The Mo atom has the largest magnetic moment and the c-Mo-TCNE catalyst features the smallest magnitude of limiting potential. Thus, the magnetic moment can be used as an effective descriptor for eNRR on c-TM-TCNE catalysts. The present study opens a way toward the rational design of highly efficient electrocatalysts for eNRR with novel two-dimensional functional materials. This work will promote further experimental efforts in this field.