Screening of metal–organic frameworks for efficient electrocatalytic nitrogen reduction

In this work, 44 metal–organic frameworks (MOFs) are screened for efficient electrocatalytic nitrogen reduction reaction (eNRR). The isosteric heats of N 2 adsorption on the 44 metal active centers of MOFs are calculated by the grand canonical Monte Carlo method. It is found that p‐block‐elements exhibit the highest N 2 affinity among all screened elements, implying their excellent catalytic potentials for eNRR. Furthermore, the Al element is preferentially chosen as the metal center of MOFs (MIL‐53 (Al)) owing to its relatively low toxicity and cost. Combined in situ Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis with theoretical calculation, we found that N 2 is mainly attracted by the bridging oxygen of Al‐O‐Al structure in the MIL‐53 (Al). The optimized MIL‐53 (Al) shows a superior activity with the NH 3 yield rate of 74.55 ± 1 μg h −1 mg cat −1 at −0.3 V vs. Reversible Hydrogen Electrode (RHE), to our best knowledge, which is currently the highest activity of MOF‐based catalyst for eNRR reported in the literature.