Zhu Xiaojuan, Wang Yi-Chi, Qu Kaiyu, Song Leyang, Wang Jing, Gong Yushuang, Liu Xiang, Li Cheng-Fei, Yuan Shiling, Lu Qipeng, Wang An-Liang
Key Laboratory for Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, China.
Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, School of Materials Science and Engineering, Tsinghua University, Beijing, China.
Nat Commun. 2025 Jul 1;16(1):5742. doi: 10.1038/s41467-025-61232-z.
Single atom alloys (SAAs) with maximum atomic efficiency and uniform active sites show great promise for heterogeneous catalytic applications. Meanwhile, crystal phase engineering has granered significant interest due to tailored atomic arrangements and coordination environments. However, the crystal phase engineering of SAAs remains challenging owing to high surface energy and complex phase transition dynamics. Herein, RuCo SAAs with tunable crystal phases (hexagonal-close-packed (hcp), face-centered-cubic (fcc), and hcp/fcc structure) are successfully synthesized via controlled phase transitions. These SAAs exhibit distinct crystal phase-dependent performance towards nitrate reduction reaction (NORR), where hcp-RuCo outperforms its counterparts with a NH Faradaic efficiency of 96.78% at 0 V vs. reversible hydrogen electrode and long-term stability exceeding 1200 h. Mechanistic investigations reveal that the hcp configurations enables shorter Ru-Co distances, stronger interatomic interactions, and more positive surface potential compared to hcp/fcc-RuCo and fcc-RuCo, which enhances the NO adsorption, reduces the free energy barrier, and suppresses competitive hydrogen evolution.
具有最大原子效率和均匀活性位点的单原子合金（SAA）在多相催化应用中显示出巨大潜力。同时，由于定制的原子排列和配位环境，晶相工程引起了广泛关注。然而，由于高表面能和复杂的相变动力学，SAA的晶相工程仍然具有挑战性。在此，通过可控相变成功合成了具有可调晶相（六方密堆积（hcp）、面心立方（fcc）和hcp/fcc结构）的RuCo SAA。这些SAA对硝酸盐还原反应（NORR）表现出明显的晶相依赖性性能，其中hcp-RuCo优于其对应物，在相对于可逆氢电极0 V时的NH法拉第效率为96.78%，长期稳定性超过1200小时。机理研究表明，与hcp/fcc-RuCo和fcc-RuCo相比，hcp构型具有更短的Ru-Co距离、更强的原子间相互作用和更正的表面电位，这增强了NO吸附，降低了自由能垒，并抑制了竞争性析氢。
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