Coronene-Based 2D Metal–Organic Frameworks: A New Family of Promising Single-Atom Catalysts for Nitrogen Reduction Reaction

Electrochemical nitrogen reduction reaction (NRR) is becoming increasingly important for ammonia (NH 3 ) synthesis, but the development of effective electrocatalysts remains a great challenge. Here, by means of extensive first-principles calculations, we systematically study the potential of coronene-based two-dimensional (2D) metal–organic frameworks (TM–PTC, TM = Fe, Sc, Ti, V, Cr, Mn, Co, Ni, Cu) as single-atom catalysts for dinitrogen (N 2 ) fixation. Our results show that the gas phase N 2 can be readily reduced to NH 3 on V/Fe–PTC through the enzymatic/distal mechanism with a quite low overpotential of 0.60/0.53 V. The underlying physics for the excellent NRR performance is discussed in detail. Moreover, the competing reaction of hydrogen evaluation reaction (HER) is dramatically suppressed in Fe–PTC, endowing them with high selectivity and thus rendering them ideal for NH 3 synthesis. This work not only provides efficient electrocatalysts for NRR under mild reaction conditions but also helps guide the future development of single-atom electrocatalysts.