Screening of Transition-Metal Single-Atom Catalysts Anchored on Covalent–Organic Frameworks for Efficient Nitrogen Fixation

Two-dimensional (2D) covalent–organic frameworks (COFs) offer abundant hollow sites for stably anchoring transition-metal (TM) atoms to promote single-atom catalysis (SACs), which is expected to overcome the poor stability of SACs on conventional substrate materials. Using first-principles calculations within density-functional theory, a number of TM atoms embedded on a 2D COF Pc-TFPN (TMPc-TFPN) as SACs for ammonia synthesis under ambient conditions are investigated. Through a “five-step” screening strategy, WPc-TFPN is highlighted from 26 TMPc-TFPNs as the best SACs for nitrogen reduction reaction (NRR) with a low limiting potential of −0.19 V. Meanwhile, multiple-level descriptors are developed to uncover the origins of NRR activity, among which a simple descriptor φ that involves the electronegativity and number of d electrons of TM atoms shows volcano plot trends of limiting potential of NRR. This work provides a rational strategy for fast screening SACs for the electrochemical N₂ fixation using 2D COFs containing TM-N₄ units as host materials, which could also be applied to other electrochemical reactions.