Rational Modulation of Single Atom Coordination Microenvironments in a BCN Monolayer for Multifunctional Electrocatalysis

Abstract Single‐atom (SA) catalysts (SACs) have demonstrated outstanding catalytic performances toward plenty of relevant electrochemical reactions. Nevertheless, controlling the coordination microenvironment of catalytically active SAs to further enhance their catalytic oerformences has remained elusive up to now. Herein, a systematic investigation of 20 transition metal atoms that are coordinated with 20 different microenvironments in a boroncarbon‐nitride monolayer (BCN) is conducted using high‐throughput density functional theory calculations. The experimentally synthesized ternary BCN monolayer contains carbon, nitrogen, and boron atoms in its 2D network, thus providing a lot of new coordination environments than those of the current C x N y nanoplatforms. By exploring the structural/electrochemical stability, catalytic activity, selectivity, and electronic properties of 400 (20 × 20) TM‐BCN moieties, it is discovered that specific SA coordination environments can achieve superior stability and selectivity for different electrocatalytic reactions. Moreover, a universal descriptor to accelerate the experimental process toward the synthesis of BCN‐SACs is reported. These findings not only provide useful guidance for the synthesis of efficient multifunctional BCN‐SACs but also will immediately benefit researchers by levering up their understanding of the mechanistic effects of SA coordination microenvironments on electrocatalytic reactions.