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

作　　者：Zhengqin Zhao Jinbo Hao Baonan Jia Xinhui Zhang Ge Wu Chunling Zhang Long Li Shuli Gao Yirong Ma Yuanzi Li Pengfei Lu 

机构地区：[1]School of Science,Xian University of Architecture and Technology,Xi'an 710055,Shaanxi,China [2]State Key Laboratory of Information Photonics and Optical Communications,Beijing University of Posts and Telecommunications,Beijing 100876,China [3]School of Electronic Engineering,Beijing University of Posts and Telecommunications,Beijing 100876,China [4]School of Integrated Circuits,Beijing University of Posts and Telecommunications,Beijing 100876,China

出　　处：《Journal of Energy Chemistry》2023年第8期79-89,I0004,共12页能源化学（英文版）

基　　金：supported by the Natural Science Basic Research Program of Shaanxi (No. 2023-JC-YB-065);the Fund of State Key Laboratory of IPOC(BUPT)(No. IPOC2019A013);the Natural Science Foundation of Shaanxi Province (No. 2021JM-371);the Open-Foundation of Key Laboratory of Laser Device Technology,China North Industries Group Corporation Limited (No. KLLDT202103);the Project funded by China Postdoctoral Science Foundation(No. 2022M720516)。

摘　　要：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 A 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.

关 键 词：Carbon-based nano-materials MACROPORE Single-atom catalyst Multifunctional electrocatalyst First-principles calculation 

分 类 号：TQ426[化学工程]