Jin Xiangrong, Chang Mengyao, Sun Hao, Chang Chun-Wai, Sendeku Marshet Getaye, Li Yajie, Wang Maoyu, Fang Jinjie, Li Yizhe, Zhu Qingyi, Li Boyuan, Yu Jiage, Liu Yafei, Chang Zheng, Zhang Guoxin, Zhuang Zhongbin, Bai Lu, Ma Qing, Feng Zhenxing, Liu Wen, Li Jiazhan, Sun Xiaoming
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States.
J Am Chem Soc. 2025 Jan 22;147(3):2689-2698. doi: 10.1021/jacs.4c14760. Epub 2025 Jan 8.
Diatomic catalysts featuring a tunable structure and synergetic effects hold great promise for various reactions. However, their precise construction with specific configurations and diverse metal combinations is still challenging. Here, a selective etching and metal ion adsorption strategy is proposed to accurately assign a second metal atom (M) geminal to the single atom site (M-N) for constructing diatomic sites (e.g., Fe-Pd, Fe-Pt, Fe-Ru, Fe-Zn, Co-Fe, Co-Ni, and Co-Cu). In this strategy, hydrogen peroxide selectively etches the positively charged carbon atoms near the M-N moiety (denoted as α-C) and produces vacancy, which could trap the M at the subsequent adsorption step. These catalysts show optimized electronic structure and enhanced oxygen reduction activity compared to single-site counterparts, and the representative Fe-Pd-NC and Co-Fe-NC catalysts stand as the most active oxygen reduction reaction catalysts (half-wave potential of 0.92 and 0.91 V, respectively). The selective etching of α-C in single-atom catalysts reported here represents a new post-treatment strategy for the targeting synthesis of diatomic sites.
具有可调结构和协同效应的双原子催化剂在各种反应中具有巨大潜力。然而，精确构建具有特定构型和不同金属组合的双原子催化剂仍然具有挑战性。在此，我们提出了一种选择性蚀刻和金属离子吸附策略，用于将与单原子位点（M-N）相邻的第二个金属原子（M）精确地定位，以构建双原子位点（例如，Fe-Pd、Fe-Pt、Fe-Ru、Fe-Zn、Co-Fe、Co-Ni和Co-Cu）。在该策略中，过氧化氢选择性地蚀刻M-N部分附近带正电的碳原子（记为α-C）并产生空位，该空位可在随后的吸附步骤中捕获M。与单原子催化剂相比，这些催化剂表现出优化的电子结构和增强的氧还原活性，代表性的Fe-Pd-NC和Co-Fe-NC催化剂是活性最高的氧还原反应催化剂（半波电位分别为0.92和0.91 V）。本文报道的单原子催化剂中α-C的选择性蚀刻代表了一种用于靶向合成双原子位点的新型后处理策略。
