Pyrrole-type TM-N3 sites as high-efficient bifunctional oxygen reactions electrocatalysts: From theoretical prediction to experimental validation

作者：Chunxia Wu, Yanhui Yu, Yiming Song, Peng Rao, Xingqi Han, Ying Liang, Liqiang Jing, Kai Zhang, Zhenjie Zhang, Peilin Deng, Xinlong Tian, Daoxiong Wu · 发表于：Journal of Energy Chemistry · 年份：2025 · DOI：10.1016/j.jechem.2025.01.002 · 被引用次数：22 · 研究领域：Electrocatalysts for Energy Conversion、Fuel Cells and Related Materials、Electrochemical Analysis and Applications

Efficient catalysis of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for the rechargeable zinc-air batteries (R-ZABs). However, challenges remain due to the scarcity of effective bifunctional electrocatalysts and limited understanding of the structure-activity relationships. Pyrrole-type single-atom catalysts (SACs) with unique electronic structures have emerged as promising electrocatalysts. In this work, we combine density functional theory (DFT) calculations and experimental studies to systematically explore the structure-activity relationships and potential of pyrrole-type transition metal-N 3 (TM-po-N 3 ) as bifunctional catalysts. DFT calculations reveal that differences in the dependence of ORR and OER activities on the free energy of adsorption of reaction intermediates significantly affect the TM-po-N 3 bifunctional activity and identify magnetic Cu-po-N 3 as the best candidate. The bifunctional activity of Cu-po-N 3 originates from interactions between spin-polarized out-of-plane Cu_3 d and O_2 s +2 p orbitals. Theoretical predictions are validated experimentally, showing that the synthesized Cu-SAC/NC exhibits excellent bifunctional performance with a small potential gap of 0.666 V. Additionally, the assembled R-ZABs display a high-power density of 170 mW cm −2 and long-term stability, with the charge-discharge voltage gap increasing by only 0.01 V over 240 h. This work provides new insights into the design of efficient bifunc...