Transition metal embedded in nonmetal-doped T-carbon [110]: A superior synergistic trifunctional electrocatalyst for HER, OER and ORR

The design of efficient and low-cost multifunctional electrocatalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is critical for the development of clean energy. Two-dimensional (2D) carbon-based nano-materials are becoming more and more popular in heterogeneous catalysis due to their cost-effective and multi-scale tunability as single-atom catalysis (SACs) substrates. In this paper, by using first-principles calculation, we designed and demonstrated a novel macropore T-carbon [110] (TC) monolayer as 2D electrocatalyst substrate for HER/OER/ ORR, and the synergistic modification of the transition metal and nonmetal atoms (TM-X) were investigated to enhance the multifunctional electrocatalytic performance. We screened out the Co embedded in N-doped TC (Co3@N-TC) from 30 TM@X-TC monolayers as a trifunctional electrocatalysts, which exhibits superior performance for HER/ORR/OER on both thermodynamic and kinetic scales, and with excellent thermal and electrochemical stability. Then, the TC monolayer is naturally macropore with a diameter of 5.36 angstrom and exhibits excellent adsorption capacity for the intermediates and products of the redox reactions. Moreover, we revealed the origin of the electrocatalytic activity using the crystal orbital Hamilton population (COHP) and the molecular orbitals (MOs). The d orbital of Co3@N-TC is significantly hybridized with the p orbital of the intermediates, so that the lone electrons initially occupied in the antibonding state pair up and occupy the downward bonding state, allowing *OH to be appropriately adsorbed onto the TC monolayer. This work not only demonstrates that the TM@X-TC monolayer is a superior synergistic trifunctional electrocatalyst, but also reveals a macropore monolayer material with potential applications in electrocatalysis. (c) 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.