Template-Sacrificing Synthesis of Well-Defined Asymmetrically Coordinated Single-Atom Catalysts for Highly Efficient CO 2 Electrocatalytic Reduction

作者：Ming Huang, Bangwei Deng, Xiaoli Zhao, Zheye Zhang, Fei Li, Kanglu Li, Zhihao Cui, Lingxuan Kong, Jianmei Lu, Fan Dong, Lili Zhang, Peng Chen · 发表于：ACS Nano · 年份：2022 · DOI：10.1021/acsnano.1c07746 · 被引用次数：172 · 研究领域：CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion、Ionic liquids properties and applications

Although various single-atom catalysts have been designed, atomically engineering their coordination environment remains a great challenge. Herein, a one-pot template-sacrificing pyrolysis approach is developed to synthesize well-defined Ni–N 4 –O catalytic sites on highly porous graphitic carbon for electrocatalytic CO 2 reduction to CO with high Faradaic efficiency (maximum of 97.2%) in a wide potential window (−0.56 to −1.06 V vs RHE) and with high stability. In-depth experimental and theoretical studies reveal that the axial Ni–O coordination introduces asymmetry to the catalytic center, leading to lower Gibbs free energy for the rate-limiting step, strengthened binding with *COOH, and a weaker association with *CO. The present results demonstrate the successful atomic-level coordination environment engineering of high-surface-area porous graphitic carbon-supported Ni single-atom catalysts (SACs), and the demonstrated method can be applied to synthesize an array of SACs (metal–N 4 –O) for various catalysis applications.