Abstract

Abstract Searching for highly efficient, stable, and cost‐effective electrocatalysts for water splitting and oxygen reduction reaction (ORR) is critical for renewable energies, yet it remains a great challenge. Here, by performing an unbiased structural search and first‐principles calculations, the electrocatalytic performance of the emerging 2D transitional‐metal carbides, MC 2 (M represents the transition metal of Ti, V, Nb, Ta, and Mo, C is carbon), is systematically investigated. Owing to their super stability and outstanding electronic conductivity, fast charge transfer kinetics is allowed during catalysis. Specifically, NbC 2 , TaC 2 , and MoC 2 possess excellent hydrogen evolution reaction (HER) performance under the reaction by the Volmer‐Heyrovsky mechanism. Moreover, taking advantage of the dual‐active‐site catalytic mechanism for oxygen evolution reaction (OER) and ORR over traditional single‐active‐site mechanism, TaC 2 presents promising bifunctional electrocatalytic activity with a low overpotential of 0.06 and 0.37 V for HER and ORR, respectively. Meanwhile, the low overpotential endows MoC 2 remarkable multifunctional electrocatalytic performance in overall water splitting (0.001 V for HER, 0.45 V for OER) and ORR (0.47 V). These intriguing results demonstrate the robust applicability of MC 2 monolayers as effective electrocatalysts.